Well this was one hell of a work out (over 3 weeks!). But glad to finally get it outta my face!
Really pleased with how the jacket and shirt turned out with the texture overlays :D (I think I just had an idea for a new tutorial!)
Photoshop CS5 + 20 hours or so.
Airbrush + Texture brushes.
Dodge/Burn and Sharpen/Blur for finishing touches!
Original Ref: http://celebritywonder.ugo.com/event/The_World_Premiere_of_%27Captain_America%27/43641311189003-b071911a-1575.html