Quick update... Thanks again for all the recommendations.
Well went to my local store and was all prepared to buy the trade of Ultimate Spider-Man Vol. 1 but alas they were out of Volume one. So I picked up Spider Man: Blue (pretty much based on Loeb and Sale since they wrote one of my favorite Batman stories) and was absolutely blown away. It was a genuinely moving and exciting arch, with some stunning visuals. It's making me rethink whether I want to invest in Ultimate Spider-Man or just hop on the train with the most current exploits of the Amazing Spider-Man. I also enjoyed them so much that I went out and got Hulk: Gray and Daredevil: Yellow, I'm half way through Hulk and while it's not as good as Spider-Man... it's still pretty damn good and I look forward to Daredevil.
Now on to Captain America, this was one of the most pleasant surprises I've had in my 3 or so years of reading comics. Bruebaker's first trade was a blast and if the quality keeps up, I'll be hooked for the entirety. Cap just really surprised me as a character he is much more deep and much less of a walking cliche than I expected. After reading Bruebaker's first trade, I found Waid's "Man out of Time" and read through it in one sitting. It was great as well and I loved the angle of Cap being a lost soldier trying to find his way in a world that has shunned a lot of his morals.
So far my exploits into Marvel has been immensely positive and I may just end up cutting some of my current DC pulls to pick up a few more Marvel titles.
Nice, glad you're enjoying it. Spider-Man: Blue is a story I've heard good things about.. as I understand it relates more to Peter Parker and his relationships than to Spider-Man himself?
Anyway, I still would suggest reading Ultimate Spider-Man - it really is good.
Also I noticed that a blog on CBR has just finished a list of the top 50 Spider-Man story arcs (Voted by fans) - it might be worth having a look:Link
A lot of the higher ranking ones are a bit older - but you shouldn't let that put you off! They're really good!