I think for a starter set, this set is excellent, not only for the value of how much you get, but also for the models themselves. Even the models I was really unsure of.... like the Dark Angels Company Master, I liked much more after getting a closer look at it.
I am one of those that never bought the Assault on Black Reach set, because it never appealed to me. Sorry Ork fans, but it was much harder to find Ork players around here to split with than it is Dark Angels and Chaos Marines. To be honest, even without a split, there are not many models in the Dark Vengeance that I could not use somewhere in my armies. While Assault on Black Reach was a good value, I think that Dark Vengeance will far out perform it.
By far my personal favorites are the Dark Angels Librarian and the Chaplin. On the Chaos side of things, I really like several of the cultists, like the heavy stubber model and flamer. If these chosen are a sign of what is to come with future Chaos Marine models, I see them becoming very popular. I like them a lot.