Here's the Stewart-Macdonald explanation:
250K pots give a slightly warmer tone than 500K because the 250K bleeds off some of the high frequencies.
250K = warmer
500K = brighter
1 Meg = brightest
Usually, 250K pots are used with single-coil pickups and and 500Ks are used with humbuckers. If you want to hear your guitar "wide open" with all the highs, try 1 Meg pots.
I just put new humbuckers in my bass with 250K pots and flatwound strings. The tone is beautiful and warm but there are times I KNOW I'm gonna need more sparkle than what this setup will give me. I going to switch out the pots to 500Ks this weekend to see if I can't get some of my highs back.