Yea, I have a vinyl background on my 29. Looks good, just gotta put it on like a decal with water and 'squeegee' it tight to the glass, otherwise you'll get air bubbles when viewed from the sides.
For fish yea, a pygmy angel would be cool, a flame angel with it's bright red would contrast nicely with the bright blue and yellow tangs. A leopard wrasse would be awesome, but I'd wait for the tank to establish a bit. Or my last thought, 2 or 3 anthias (lyretails are my fav. and easiest to keep). Though you'd have to have a fairly capable skimmer and be able to feed 2/3x a day.