You can FOIA the Government Master File through the Interdepartmental Radio Advisory Committee (IRAC), which is a unit within NTIA. They will respond quickly and send you a Windows-compatible CD-ROM that acts like an app (in other words, you launch some software on the disc and it allows you to query the database and generate some reports). They'll also send you a bill for $35.
The issue is that the database is scrubbed and doesn't contain many Federal frequency assignments, only non-government assignments for which federal users also hold authorizations. (Think state mutual aid frequencies, local or state fire channels for areas near Federal installations, etc.) So while it contains quite a number of records, few exclusively-Federal assignments are included.
While the full database is not classified, it is exempt from public release because it contains specific assignments that may be classified and because of the concern that people will construct a matrix of publicly-releasable information and then investigate the remaining holes in the matrix (as hobbyists have been doing since time immemorial). Individual agencies control the status of their own assignments, and there have been successful efforts to FOIA frequency lists from them. I would not be optimistic about getting LE-related assignments from anyone, though.
I have to take some responsibiity for this situation. Back in 1982-83 I requested all publicly releasable assignments in the Government Master File and received them on microfiche with very few fields included. Bob Grove had just published his Federal Frequency Directory that listed hundreds of thousands of frequencies with agency and location (but no usage details). When I asked for the "bureau" field that indicated which component of an agency used an assignment, as well as for the "notes" field which can be quite revealing, they denied my request and declared the database exempt from public release under FOIA. My bad, I asked for too much.