>>53485760I had fun psychoanalyzing yesterday, so I'll bite.
I guess to preface, Ash and Misty were written somewhat realistically in the OS as a couple of kids who are starting to develop feelings for one another, but don't really have the emotional depth or maturity to fully understand or express them. Ash as a character is dense/harder to read, which is why Rudy and Danny were written into the Orange Islands arc to show his jealous streak, and maybe drive it home to the audience.
The constant bickering is meant as a display of G rated sexual tension, as lampshaded by Tracy. Less heavy handed is the impulsive and frequent touchy feely interactions between them, which shows indicates a great deal of comfort with one another. But the defensiveness they show when called out by others as potentially being anything more than friends indicates that they don't want to think about what those interactions might actually mean.
To get to the question you raised, I think Misty's probably supposed to be aware after the 2nd movie, where her coming to terms with her feelings after being made fun of by Melody is the resolution to an entire subplot. But we also don't get much chance to find out where that could have gone afterwards, because Johto dials back the Pokeshipping, and it all but evaporates in AG.
The only thing you could draw conclusions from is the bit where she turns down Georgio when he asks her out. Her busting a forehead vein when Psyduck starts laughing at her non-response to the question about liking someone else shows that she knows that her Pokemon can read her like a book, even if the two human characters aren't entirely in the loop.