Do Proportioning Valves Wear Out?

Nope, they don't wear out.

And, they're not even steel, so the only rust in them will be deposited from the brake fluid carrying it from other places.

They do plug up from all the crud in the lines, but if you clean it out well it shouldn't be an issue.

X2 They are made of brass and can be cleaned out and I believe internals can be replaced.