COOL!
Good to know my site is back online - it was down for quite a few days....
Anyway:
Volume - unless you have an area that is like a bowl (spare tire well, etc), it's difficult to measure volume before building. You can try filling a garbage bag with styrofoam peanuts, and shoving the bag into the area you will mold for your enclosure, and see what you get. Beyond that, the best thing to do is to build the mold, making it a bit larger than you need. Then you can use the styrofoam peanut trick - just fill the mold as best you can, and then pour the peanuts into a carboard box (easy to measure volume) and see what you've got.
You can also do this once the enclosure is nearly completed. If you're concerned about airspace that much, make the enclosure a bit too large - you can always add material (chunks of wood, etc) inside to take up airspace.
Overall, sealed enclosures are very tolerant of differences in airspace, and I wouldn't go crazy worrying about getting it exactly .8.
A "Wall" - a wall is unnecessary. There is no need to separate your subs. The ONLY purpose it serves is to protect one sub if the other should blow - so that the single sub is not now operating in too-large of an airspace that could be damaging. There is NO such thing as the "push-pull" effect or subs "fighting" each other in a common airspace. You don't need to separate subs as long as they are playing the same material (wired mono).
I'm not really sure how you'd go about doing it - other than it will have to be planned out well in advance. It'll also be very difficult to get the airspace of each chamber the same - something that IS important.
Personally, I wouldn't bother with it.
Finishing - sanding and paint prep will probably take longer than the construction. First roughen up the surface with some heavy grit paper - something like 40 grit oughtta do the trick. Then slather body filler (Bondo) all over the thing, let it cure, and then sand sand sand. Your object is to get it a smooth as humanly possible. It's gonna take a lot of time. Start with heavy grit paper, and work it down to the finest you can stand to use - I've read that 220 grit is good enough though. Using a high-build primer is a good idea, too - this will fill in the tiny pinholes the Bondo leaves behind.
Once you've got it smooth and all the imperfections are gone, prime it and paint it.
Simple, but very time consuming.
~HH