Alright I figured I'd update you on my #1's.

A-Babies vs X-Babies

An adorable one-shot with Baby Captain America fighting Baby Cyclops over a Bucky Bear doll.

Annihilation Prologue

I didn't follow this at all, sorry. Too grand for a starting point, not enough familiar characters for me.

Avengers, Vol 1

I had to read this one, the original Avengers meeting up. I love these old comics, with Stan Lee explaining what is happening in EVERY SINGLE PANEL.

Baby's First Deadpool

Another one-shot, a fake coloring book / story book about Deadpool

Hawkeye (2012)

I have a friend who is in love with the Matt Fraction Hawkeye series. You can really see why. Simple art, simple story of what Hawkeye does when he's not Avenging.

Iron Man, Vol 4

Figured I'd read a recent Iron Man. I did not care for the art on this one. It was kind of CG, very weird.

Marvel's Iron Man 3 Prelude

I'm a sucker for movie tie-ins, actually bought the 2nd issue of this (of 2). It's pretty good.

Marvel's The Avengers Initiative

A simple one-shot that shows what the Avengers were up to just before the Avengers Movie.

New Avengers: Illuminati

I misremembered the recommendation of Anniliation, which caused me to download this one. It's a Road To The Civil War book, and I really liked it. I'd love to read Civil War, but it looks like its spread out across way too many books.
http://en.wikipedia.org/wiki/Civil_War_(comics)#Comic_tie-ins

Superior Spider Man

I read about how the last Spider Man series ended, so I'd be interested to check out the newest one. Even without having read any Spidey, this grabbed my interest. Of all I've read, this is the one I might keep reading.

I wish I had a lot more disposable income...