Reading that thread about Bleach made me want to read some fanfics for it where the characters DO develop relationships and in my search, I found this gem.
This is easily the best Bleach fanfic I've read, the characters act nearly identical to what I remember from the series. Author did an amazing great job with the personalities, they hit the nail on the head.
28 chapters at about 4-8k words each.
After the Aizen arc ends in Karakura Town
Gets full of fluff 'n' shit at chapter 14 or so but still manages to be interesting, focusing primarily on character development and relationships between characters. Funny moments involving Renji, Ichigo's dad, and Byakuya made me laugh out loud.
Secondary Main Characters (Show up a good bit but never from their perspective):
I really do suggest this to anyone who thought Bleach had potential it never lived up to or even those who thought it was good. It surprised me.