Good day,
With the transfer case, it really depends on which one you have in the vehicle. Yours more than likely takes ATF, but I would have to look up your specific truck to find out if yours takes just ATF. Some take GM AutoTrac II fluid. However, either way, most service intervals depend on the fluid itself being used and the manufacturer recommendations from that fluid. That being said, the majority of ATF service intervls for the transfer case are for 100K under normal service conditions and 50K under severe duty service.
That being said, there is also an issue with the transfer case pump shim inside the tc. It has a thin edge on the sides and there is one spot inside there that it will rub all the way through the front housing of the tc and leak fluid. If that accurs you are facing either rebuilding it or replacing it.
Check out this DIY installation Thread I made for the "Pump Rub" issues.
Beyond the transfer case, making sure that your Ujoints are good should be about it. There isn't much you can do to maintain the electrical parts, when they go you just have to replace them.