XPS foam board has an R-value of 5 per inch. Two layers of 1/2" XPS (@ $15 per sheet X2) will still give you just R-5 (they are rounding 2.5 up to 3 for marketing purposes) but will be a lot more expensive than a single layer of 1" XPS (@ $20 per sheet). After a couple of years, the blower gases used for XPS (which have a lower thermal conductivity than ordinary air) will leech out and be replaced with ordinary air, lowering the R-value to about 4 per inch, about the same as EPS foam board. So arguably, you might as well just start with EPS.
Polyiso board has an R-value of 6.5 per inch, but this is only at 75°F. In lower temperatures the R-value drops drastically - it's only R-2 per inch at 15°F (these values are from the company's own literature). So this stuff is hideously bad if you're trying to survive cold temperatures, but as good as it gets if your primary concern is surviving hot weather.
Rock wool and fiberglass are worse than any of the boards, about R-3 per inch, and they have effectively no compression resistance.
The best insulating material you could possibly use is aerogel, which is about R-10 per inch. But it's hideously expensive and has no compression resistance whatsoever, so using it for a subfloor would be difficult and costly.
What you use is really just a function of how tall you are and how tall your bus is. My bus is 6'7" from steel floor to the middle of the ceiling and I'm 6'0", so I was able to put 2" XPS on the floor and 3/4" plywood (I'll also have 5mm underlayment and 1/8" vinyl floor planks), and 1.5" XPS between the ribs with 3/4" XPS inside the ribs (along with 5mm underlayment as the ceiling panels). This leaves me with an internal ceiling height of 6'3" - I would say having 2" or 3" over your head is about the bare minimum you'd need to be able to walk comfortably inside your bus, but you could maybe go a little bit less.
6'7" buses seem to be pretty rare - only the high-ceiling Internationals and Thomas C2s have that. Blue Bird high-ceilings are 6'5" and Thomases (other than the C2s) are 6'4", and the short versions of all these buses are really short, like 6'1" or 6'2". This is why roof raises are so common in the skoolie world (I feel very fortunate that I've managed to get away without doing it, but I was prepared to do it if it had proven necessary).