Millennium Actress - Probably the best anime film I've ever seen. It has great animation, really amazing music by Hirasawa Susumu, and it has a touching story.
http://www.millenniumactress-themovie.com/
Scrapped Princess - Possibly one of the best animes out there. It's licensed but DVDs are coming out
http://www.animenfo.com/animetitle,1...ed_prince.html