A polyswitch is just a special thermistor, which is just a special resistor. And remember that the component doesn't care what ground is, it just cares what it sees applied to it. Applying -20, 0 across a resistor is just like applying 0, 20 across it - it just sees that one side is 20V higher than the other.
One thing to keep in mind is that you don't just need to block currents rail-ground, but also rail-rail. Many polyswitches have pretty low voltage ratings and many dual rail systems have pretty high voltages. Make sure it has a good safety margin around the total rail-rail voltage.
(Clarification: Ideally, if the fault current is rail-rail, both polyswitches will trip and share the blocking voltage. They are resistors, after all, even when tripped. I don't like to count on that, though.)