Actually, I think it would be the reverse in this case. A 250k ohm pot has less ohms than a 500k pot, which the 250k will require two 250s in order for it to work like a regular 500, volume-wise. Tonally, however, it sounds different.
I myself have thought of an idea that involves two volume controls on a single humbucker, one 250k and one 500k. The 250k is placed before the 500k, and acts as a "signal choke" for hot humbuckers to roll off the volume of the signal, before using the 500k as a master volume. Has this been done before? I don't know if it has or not.