PVA is in a lot of glues. I don't really use it... but some people use Modge Podge or similar stuff to 'seal' the foam. If I need a re-enforced area within a foam piece (connection point, let's say), I just use 2-part epoxy coating before the plasti-dip on the piece.
Now that I've seen your costume, I'm thinking FOAM for most of it. The tight fit of the legs especially, would be a REAL challenge (both to build and wear).
I should point out isusuperman's
thread on sewing foam armor... It's a VERY unique idea, but it might work well to replicate that skin-tight armor you want to create.
Here's the painting technique I'm using on my son's armor...
For hardened pieces I just use a good primer and then the auto paint. If it needs it (depending on paint type it might), hit it with a gloss coat as well.
For foam pieces I paint them in this order:
1.) 2-3 coats of plasti-dip
2.) 2 coats of adhesive promoter
3.) 2 coats of final paint color (Duplicolor colors I'm using: Dark Cherry Metallic & Sunburst Gold)
4.) IF it needs some extra shine, hit it LIGHTLY with some clear gloss for plastics (auto part stores carry this for flexible bumpers and stuff).
The trick with the gloss is to keep it LIGHT... just enough to have it shine without putting a thick layer on it that will crack. Also, you can mostly aim it on the surface... don't bother hitting the edges of the foam. That's an area you don't see much of and it's also the MOST flexed area on the piece.
Hope that helps! Let me know if you have any other questions!