Bleach will kill microorganisms on the surface, but it doesn't penetrate very far. If you want to let the pumpkin decay to the point that the structure starts to break down, bleach won't halt the decay. You would need to preserve it using a method that preserves biological specimens. I know immersing it in formaldehyde is often used. I think there is also a way to immerse it in successively less diluted alcohol. I'm not up on the subject, but it would be easy to research.
Once you stop the decay and preserve it, it probably will be rubbery (at least the decayed areas), not rigid like a fresh pumpkin. It will also probably be very wet and difficult to dry to the point that you could paint it, at least without dehydrating it, which would change its appearance. To have something solid, you might need to create a mold of it and then cast a replica. There are relatively inexpensive ways to do that, which could make a good subject for another question.
As for the chrome effect, I have some ideas as well:
Spray-painting the result would work to get a chrome look. You wouldn't be limited to a specialty paint. You can buy chrome spray paint inexpensively at paint, hardware, or auto supply stores.
It might be less work to just make the entire Jack-o-lantern from clay.