Bribing the guards is not prohibited? But then, the only thing the prisoners have to offer is a few hats, so I guess that's out of the question
Your original question said 'no cheating' so I'll assume that was an incomplete qualification of 'cheating'
Also, what is the probability of successfully digging a tunnel or finding another escape route? The prisoners could keep their eyes open for something, but only take the opportunity if it's a 'sure thing' thus increasing their chances above 50%.
Other than that, as far as I can see, it will only ever be 50%.
I'm assuming (yes, a bad habit) you're thinking that the 'guesser' can do something better than 50-50 by looking at the number of hats of different colours, then basing his guess on this (e.g. if more than 3 hats are white, guess red, if more than 3 hats are red, guess white) Since each hat is picked independently, and has it's own equal, independent probability of being either red or white*, it will, no matter what the colour of the hats infront of the guesser, ever be possible to get the answer right 50% of the time.
The only information available is the colour of those 6 hats, but the colour of everyones hat, except that of the single guesser, is irrelevant. If more than one person makes a guess as to their hat colour, the chance of everyone surviving lowers. But it will never be higher than 50-50.
If, like Agaricus, I've not missed something subtle, I say he's got it.
* I'm assuming that each time one of the condemned has a hat picked, another hat is added to the 'pot'(and the 'pot', suitably agitated so the next person doesn't just get the new hat that has been placed at the top) so the probability of picking the same colour remains the same each time, as stated by the question.