I think you should rethink what you're trying to do. If you're trying to optimize your performance, you're probably barking up the wrong tree.
pthread_cond_signal()
isn't even guaranteed to unblock exactly one thread -- it's guaranteed to unblock at least one thread, so your code better be able to handle the situation where multiple threads are unblocked simultaneously. The typical way to do this is for each thread to re-check the condition after becoming unblocked, and, if false, return to waiting again.
You could implement some sort of scheme where you kept your own priority queue of threads waiting, and each thread added itself to that queue immediately before it was to begin waiting, and then it would check the queue when unblocking, but this would add a lot of complexity and a lot of potential for serious problems (race conditions, deadlocks, etc.). It was also add a non-trivial amount of overhead.
Also, what happens if a higher-priority thread starts waiting on a condition variable at the same moment that condition variable is being signalled? Who gets unblocked, the newly arrived high-priority thread or the former highest priority thread?
The order that threads get unblocked in is entirely dependent on the kernel's thread scheduler, so you are at its mercy. I wouldn't even assume FIFO ordering, either.