Le Guin is a great author but I struggle to engage with her characters. Brian Aldiss I think does better? And Vinge? This is sticking to the classic era. The genre has changed and there are too many more recent excellent SF writers of character to do justice to in a post
Pohl wrote pretty well in my opinion. The psycho-therapeutic aspect of Gateway is brilliant for the sci fi of that era.
Plenty of sci fi authors wrote characters comparably with PKD, such as Zelazny, Le Guin, and Bester.