Sound of Dubstep and Generation Dubstep are both pretty mainstream compilations, with remixes of chart acts like Rihanna and Kelis sitting shoulder-to-shoulder with more underground stuff. However they do a decent job of showcasing the variety of sounds out there at the moment, and are pretty accessible too so they would make good introductions to dubstep.
GetDarker Presents: This is Dubstep Vols. 1 and 2 are less mainstream compilations but again, they do a good job of presenting some of the different styles of dubstep.
If I could only choose one then I'd say go for Sound of Dubstep as it has a good balance of mainstream and more underground tracks.