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I think Steven has the right track. There is such a difference between sub-genres and some authors assume a grounding in the genre. Charlie Stross is one of my favorite authors but a new SF reader will likely be thrown by how much he assumes of his readers.
I've been a fan of the cyberpunk subgenre since it was invented. So I'll suggest a couple of classics, Neuromancer by William Gibson and Snow Crash by Neal Stephenson (much more intended humor in Stephenson's books). If you like short stories more then maybe Vernor Vinge's "True Names" collection would work. But the whole subgenre might not be your cup of tea.
If you like aliens you might prefer Vernor Vinge's "A Fire Upon the Deep" and "A Deepness in the Sky."
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