Most Mail Processing Plants have three shifts (or tours, as they call them):
7 am - 3 pm Tour 2
3 pm - 11 pm Tour 3
11 pm - 7 am Tour 1
Each tour has a specific function that requires the use of radios, and how the channels will be used. Tour 2 is not that busy, with some of the supervisors talking on radios, and Vehicle Maintenance Facilities using them for communication, as well as transporting equipment around. Tour 3 is going to be the busiest, with collected mail going to the plants to be sorted and processed, and then distributed/loaded onto the trucks for further sorting to the assigned plants/locations to be determined (airports, other sorting plants, etc.). Tour 1 has operations such as final preparation of mail being sorted by the machines (letters going through a DPS machine [delivery point sequence which puts it in walking order for the carrier without manual sorting]) and is the second busiest time for radio usage.
Hopefully, this will help with trying to figure out what freq's are being used, etc. Also keep in mind that most plants are using analog simplex mode, and you do have to be within a quarter mile to pick up the signal with an external mobile antenna I have found out when trying to search out these types of channels. Other larger plants use repeaters and also I've been told that newer radios for USPS Plant Ops will be MotoTRBO capable, as the digital voice is far more superior and intelligible on the noisy work room/plant floor than analog voice. So, don't be surprised to hear that buzz saw type noise (and if you don't know what it sounds like, the W2SJW.com website has a number of strange radio sounds to help identify what you ae hearing) on the USPS Plant Ops channels for your local area.
In addition to monitoring the Federal VHF-Hi and UHF bands, some agencies have moved over to the Motorola DTR 900 MHz radio series as well. So, don't be surprised to see them using those as well...