I recently installed a set of S13 cams. Let me be the first to tell that you need to seriously mark the chain and the cam gears. I made the horrid mistake of not marking anything.... well about 12 hours of an install later, it was running again..... it's easily a 1-2 hour job. VERY easy... IF YOU MARK IT!!!
So don't do what I did. Mark it, Mark it, Mark it...
To answer your question, the exhaust cams have a higher lift. the S14 is cammed: 232/232 (in/ex). the S13 is 240/248 (in/ex) (i think that's right). Higher lift = valve is held open longer = more intake of air.
With each combination you gain a different set of pros/cons. Some run 240/232, 240/248 and 248/248. All depends on where you want to put the hp/torgue. I run the 240/248 and noticed a difference in the upper rpms.
I believe you have to offset the two exhaust cams by 4 teeth on the cam gears... don't ask me, that's what i've heard on multiple occasions. This is also why I shyed away from that option.
zerothread?id=109528
If you decide to pull the cams, use the JWT guide PLUS this one (which I found better than the JWT one) It's under the CAM install. It's important to notice the notch and the number of links between the two notches.
http://www.negative-camber.org....html
DID I MENTION TO MARK IT!!!