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Marinette falls for Adrien because of his kindness, yes. But also because she knows that he won't love her.
Adrien falls for Ladybug because she shows him kindness, and affection, and love. It feels like a betrayal when he finds out that it isn't actually reciprocated. He clings to it, though, because it's all he has. He isn't sure if the feelings are still there. But he tries, because he can't have taken so long to fall only to get out so quickly.
Marinette knows that Chat Noir is very loveable, but she can't bring herself to. It would be less painful on her heart. But she finds herself not wanting that, being unable to fall in love with him because he's in love with her.
Adrien likes Marinette. Maybe not romantically, but it is a possibility. He can't. He finds herself...not attracted to her in a romantic way, and it would be easier than loving Ladybug (but does he really anymore? Feelings are hard). He can't figure out why exactly...
Marinette finds herself captivated by Luka. It is easy to see the beginnings of something there, something that could become a thing. Besides - Adrien is never going to love her back (perhaps that is the appeal?).
When Luka confesses to her, though, she finds herself wavering. When she makes her choice...she isn't certain that's what she wants.
Kagami loves Adrien. And he feels obligated to love Ladybug because he fell for her first, but Kagami is in love with him, and she makes that very clear.
He's starting to love her back.
Why should Marinette feel obligated to love someone who loves her back? And...and she can't. She doesn't know how. How did she love him back, without her memories? How did she love him without those things? And...and why can't she love him now? It isn't because she loves Adrien. He loved her and she loved him.
She still loves Adrien, with most of the beats in her heart. There's another girl in his heart, though, and it will never be reciprocated. She…doesn't know whether she wants it to be. That should have been the first sign.
"Is something wrong, Marinette?" Luka asks.
"No," she answers. Why would there be...oh right.
"I can tell your heart isn't really here…"
"Wh-what do you mean, Luka?"
"You chose me, but did you want to?" He places a hand on her shoulder. She looks away. "I know that you're...you're invested in making this work, but it isn't the same."
"I know." She almost tells him "I love you." But Marinette doesn't want to be a liar.
"I need you to tell me what's happening. I can't read your mind. I just need you to talk to me. That's how we make this work."
"I," she sighs, "I would certainly tell you if I knew. But I don't have the answers."
"Then you can tell me the questions. I might not have the answers, but at least we'll be asking them together."
"Okay. I'm struggling because I was...I was wanting a relationship with you, but when you confessed to me...that desire evaporated, and I tried to cover up and pretend it was still there."
"What are you asking, then? What knowledge do you seek?"
"Why. Why am I...why is it like this?"
"You can't make yourself love someone. I know that it's awful, but we can't keep doing this. I won't...I love you, but I won't be a fool for you."
"I know." She averts her gaze again. "I'm sorry. I would if I could, and I wish I knew why I can't."
"It's okay. We can still be friends, but it might be a little rocky at first."
“Yeah. I get it.”
But even as one thread is resolved, another picks up.
Adrien and Kagami are in love. That is a fact.
Marinette is in love with Adrien. That is also a fact.
(There are a few more facts left to find - but neither have tried to look before.)
"Oh, don't you know?" Nino says, as though he isn't about to completely shatter Adrien's world, "Marinette's been in love with you for a while now."
They're watching Marinette and Alya walk away, after Marinette botches another attempt at talking to him. It makes so much sense.
Adrien doesn't fall for Marinette straight away, but once he learns that she does love him back, it's a near thing. He doesn't know about Kagami.
He searches himself, and tells Kagami that he loves Marinette not instead but in addition. And she encourages him to pursue who he loves.
So he does.
Adrien's confession should be a dream come true. But when he tells her he loves her, she tries to find those feelings again, but they've evaporated like water, leaving her with a choice.
"I can't. I loved you for the longest time, and I don't know why but my feelings for you just…vanished." She feels like she'll cry.
"That isn't how feelings should work," Adrien says, but he sounds lost and confused.
"Tell me about it," she mutters. He explained to her about Kagami, and she has to wonder why is he so devastated when he already has a girlfriend?
"Marinette, are you telling me the truth?"
"Why wouldn't I?" she retorts. She's trying to keep it together, and sometimes being polite is the cost. "I- everyone knows that I've had a crush on you since the start of the school year. You asking me out should be a dream come true. But I don't know why or how my feelings disappeared. It's like when people confess to me I stop having feelings for them."
"I think I might be the opposite," Adrien says, looking like it's something remarkable. "When I think someone has feelings for me, I reciprocate."
"So I guess we're at an impasse," she says, almost laughing. "How'd you learn?"
"Nino let it slip." Well, Marinette still trusts Nino, but she honestly doesn't know what to make of that. "And in hindsight, it makes sense."
"Well, if you only love people once you know they love you, and I only love people as long as they don't love me, we're some kind of opposites."
"I guess so," he answers, and offers his fist for a fistbump. She takes it.
In their defense, he doesn't think either of them thought of that as a form of being "aromantic," and none of them are very well educated on that sort of thing, but when Alix comes out he does more research, because he experiences love differently from regular people, and he finds out that aromantic is part of a bigger spectrum. He sends Marinette an English article with a term that sounds like how she described it to him.
And he reads something that sounds like him. Recipromantic. It's even right in the name. It's a little more niche of a label, but he likes that a word exists for people like him, and he nests it away in his heart.
Adrien's sent her an article in English. Why?
But she opens up the article anyways, and that is the right word, huh. The Internet has everything, she supposes; even a word for her experience that she thought she would be alone in.
She texts Luka to say that she found the answers, and he responds that he's happy for her. She feels a little bad, but knows that truth is more important.
Infinitely more important.