Get a copy of the ARRL study guide and get your HAM license. The books have good info in them, and if you're gonna read the whole thing you might as well get the license. There are a few non-HAM bands you can also tune into on your baofeng - GMRS, MURS, and FRS. Transmitting in these is a bit of a legal grey area though, so keep that in mind if you're going to use them. Generally speaking, so long as you're operating within the specifications of the band and not interfering with anyone else's communications I doubt anyone will complain.
As for COMSEC, it depends on what you're trying to accomplish. Radio brevity is the easiest - you can't be tracked if you aren't transmitting so keep transmissions short and to the point. For communications from a semi-permanent station, you may want to invest in a directional antenna like a yagi. This has the double benefit of making your signal stronger for the intended receiver while making it harder to detect from other directions. Naturally, you'll have to have an idea of where the other person is located before you can use it. Conversely, if you're monitoring local freqs, having a directional antenna will give you the basis for beginning your own SIGINT program, as now you can get a rough line of bearing to whatever signals you pick up