What about the timing chain? I'm reading that gm doesn't provide a maintenance cycle for timing chains, they are supposed to last the life of the truck but I'm pretty sure that 300,000 miles is more than they expected these trucks to last. Are these interference engines?
It's not likely to break. If this were an earlier engine, it might have gotten a cam gear with nylon teeth that could strip, but that's not relevant on your engine. It could wear, and many guys do change them, but this shouldn't be a priority.
I have my original timing set at over 300K miles and have no plans to change it. I did have to do it on my Buick, as it had the nylon teeth that strip. It simply stopped running while going down the highway.
I've heard conflicting info on whether a SBC is interference or not. They're certainly not interference like a newer design import engine, but I don't think the chances of piston and valve contact is exactly zero, either. Again, this isn't something you need to be worrying about. It's not a timing belt that has a mileage and time replacement recommendation, and there are no guides, pulleys, or tensioner to fail that would throw the chain.
Assuming this is a daily driver, and not a hot-rod/race-truck, and you have reason to do the water pump, then maybe think about the timing set, since you'll be there already. I only say that since you do have over 300K miles, and it was a work truck.
However, you might consider looking at the cooling system. The small block Vortec engines are known for leaking intake manifold gaskets. A pressure test is simple to do, and bad intake gaskets can let coolant into the oil or hydraulically lock the engine, or keep it from starting. Given the truck has over 300K miles, it's probably happened already and been fixed, but could happen again depending on the gaskets used. Checking this would be much higher on my list than a timing chain.