last year volunteer registration was before the first round of badge sales, but so far there's been no word about that. With Wondercon coming up soon, they may have new volunteer registration after the badge sales, but that would bring a flood of people signing up.
If you both are early registers to the volunteer pool, then you stand a good shot of both being accepted in, pretty sure it's "first come first served"
No experience necessary! You'll be given instructions as to what to do, and the area/group leaders are always wonderful people to work with and will answer any question that you have.