I've been thinking about this one....
Kristen, am I right in assuming these are either models or sort of "art shoes" you are making up for a project, or prototypes? In which case, it's not like you are actually making ready-to-wear shoes, but shoes that are more like objets d'art..... I think polymer would be a fun material for you to experiment with.
Polly, you are absolutely right about how to go about it. It's *possible* a solid polymer-clay heel, especially using the stronger brands, could hold up, (although I'll bet you actually *underestimated* how many psi it would have to withstand!), but a regular heel covered with polymer would probably work better. Especially if the polymer didn't actually cover the bottom of the heel. A thin skin of polymer could be glued on, or a larger amount molded around the heel as a base, or even carved. It would simply decorate the heel, rather than directly absorb the actual impact a "working" heel would....
And one caveat--since polymer clay must be baked (usually around 265 degrees for at least 20 minutes per quarter-inch of thickness), exercise caution when baking it on other items which may not tolerate that much heat. If you suspect the heel or the shoe itself can't be safely baked, then you could apply the polymer clay, carefully remove it (by cutting, if you've got undercutting in the molding process), bake the polymer separately, then glue onto the heel after baking.
hth,
Luann