These days I have been really loving the 1995 self-titled album from Erasure. I know they're mostly known for their 80's synth-pop hits, but this album is very spacey, complex, gorgeous, and interesting. I Say I Say I Say is also fantastic.
I think my favorite electronic group is the Pet Shop Boys and a great place to start would be their albums Very, Behaviour, Nightlife, or of course a greatest hits collection.
I also highly recommend "Technique" from New Order, "Music for the Masses" from Depeche Mode, and "With Sympathy" from Ministry.