>>53224583The first time she decided to follow him she didn't know him all that well and hadn't fallen for him or anything. Even if the bike was just an excuse it was more out of curiosity that she tagged along. Not a very high stakes negotiation, and as far as she cared he had no right to refuse, so there was zero pressure for her.
When she wanted to follow him again recently, she hadn't asked to do so for a while. Remember she nearly burst into treats when they parted ways, so traveling with him has come to mean a whole lot to her. And she actually cares what he thinks this time, so if he refuses it'll really hurt. They didn't hang out all that long in Hawaii and there were lots of other people around, and this time it's just the two of them. She can't say something like "I just want to spend more time with you" because that'd be super embarrassing.
Ash for his part seems to think it's silly she's being all coy and teases her about it, because it's not really like her. I dunno if he realizes she's crushing on him, but either way, she's one of his closest friends so her having to ask his permission to hang out is laughable. Especially after hanging out all day already. It's a good thing Pikachu played his role so well because if that'd gone on any longer Misty might have been really heartbroken (again)
tl;dr: If you think of this as a continuation from their parting ways before, where Ash was casually playful and she was seriously upset, her awkwardness makes sense.