I find it quite useful for playing about with VOR's, as I have particular trouble getting these 'straight' in my head, particularly while flying the aircraft as well.
The problem comes when I climb back into an aircraft to try the same thing - there's so much going on that I get all mixed up again. I think it'll just take time, but I'm convinced that any extra experience must be helping.
I'm not sure about FS2000, but 2002 is VERY accurate for all the VOR's and NDB's I use for my real flying in the UK. The radials and distances of airfields always seem to agree exactly with what it says in Pooleys, which is more than can be said for real life