Union Co Sheriff and Union PD recently moved their communications to Palmetto 800, the statewide radio system used by many state and local agencies. It is a digital trunked radio system, so it requires a more current scanner to listen. You can look in the Wiki Radio Models section and look for digital trunk trackers for options on scanners that will monitor this type system. The good news is that it's not a P25 Phase II system yet, and the Union County site is not simulcast,so you don't require the most expensive scanners to listen.
Union County Fire and EMS are still VHF analog that can be received by any scanner on the market.
SCHP, DNR, Spartanburg, Laurens and Chester Counties are all mostly on Palmetto 800, with fire departments in all of those counties mostly using VHF analog.
While more and more agencies are employing encryption, there is still a lot to listen to, including law enforcement, in Upstate SC.