A Shinier Silver Surfer.
 

I love my Marvel Universe Silver Surfer, and honestly, would love a new one with more articulation! Now, I already have body molds in mind [Multiple Man, of course]. But before I do that, I want to do some practice painting on the original. My problem is that he is not nearly shiny enough to be Silver Surfer! Anyone recommend any paints or a glossy finish that would work on a small figure like that? Thanks!

I know this feeling. The surfer that's packaged with Galactus is much better in terms of paint app, it's much more silver and has a cool black wash around the eyes.
I've just bought a set of Vallejo acrylics and picked up some Mithril Silver, which, after about 4 thin coats will cover even a black base coat. It's generally used for dry-brushing metal details but, in it's undiluted, straight from the bottle form, is a very good shiny silver.
You'd probably want to apply a lacquer of some sort after to seal the paint job. If you pick the right one that should give it extra sheen.

You can use Future Floor Finish.