At the headfi show in San Jose, I tried a variety of the very small portable headphone amps with my nano and shuffle, and found there was modest improvement with any of the headphones I was using (Shure, UE, Westone or Crossroads). This surprised me. Often I found it was a tradeoff e.g. a little more dynamic but a little more veiled too. I imagine that if you get one of the larger amps, especially a tubed amp, it would be real nice, but that's not portable.
Art