Well, I didn't get into anime until around 2005 so my examples will probably be more recent. I think I sort of had an anime crush on Teletha Testarossa at one point, but the first one I distinctly remember was Eruruu from Utawarerumono, followed shortly after by Yuki Nagato.
Weirdly enough, I can actually credit anime (and especially cosplay blogs) with getting me a girlfriend... I was kind of indifferent towards girls previously.