Pattern Recognition is my first brush with Gibson's work, and I've heard from multiple sources that it's his most accessible and engaging book. I can't compare it to others, but I can say that I agree about it being accessible and very engaging (but it also appeals to my 20th-century theory tastes).
Furthermore, I wouldn't count it as "sci-fi," and would instead call it a work of speculative post-9/11 fiction. There is only one element of the story that is mildly science fiction (the protagonist's "reaction" to trademarks), and it is dealt with so naturally that it ceases to be all that far-fetched (in my opinion). More importantly than any science fiction ties the book might have, it's its commentary on contemporary culture that is truly its central focus, and the most gripping aspect of the book in general.
I'm planning on reading Neuromancer, although I've been warned that it's a trip.
EDIT: by "20th-century theory" I just mean that the book actually name-drops several 20th century French theorists whom I am fond of and familiar with, so that aspect of the book appeals to me personally. I would still recommend it to anyone interested in poignant cultural criticism wrapped up in the form of a politico-economic suspense thriller.
