Hydro time is the appropriate time to do valve overhauls...it's basically the standard time, unless the valve has quit functioning for you in between hydro intervals, or the tank gets excessive use.
It's extremely straightforward and the parts for valves are readily available. A standard Thermo valve is only about $15 (retail) for parts to rebuild - seat, washers, etc, plus a couple of bucks for a new burst disc assembly (not part of the standard kit). A manifold takes three kits, if you've got the tanks twinned up.
That said, you need three tools beyond the basics that most normal guys have in their garage: a valve handle removal tool, a 1/4" precision torque wrench, and an ultrasonic cleaner.
The handle removal tool can either be purchased online, or made yourself from an old regular screwdriver and a bench grinder to put a notch in the center of the blade.
The torque wrench is required to replace the burst disc. You _have_ to get the torque right on it, or it won't function properly. Also, they're one-time install items, whereby if you remove it, you need to replace it. Modern valves use the disc-and-plug assembly as a single piece; the old valves used to have a copper washer you could just swap out, but they've essentially quit making them.
The ultrasonic cleaner's functionality should be self explanatory (and, if it's not instantly apparent how and for what you'd use it, someone else should be doing this work)