One thing that makes NAC codes useful is the "rule" regarding NAC code on a trunked voice channel. Generally, NAC on a trunked voice channel is the last two digits of the sysid plus a single digit identifying connect tone (essentially a PL code used by the trunking controller). So if you stumbled across a P25 signal and found it had a NAC of 2F1, odds are half-decent that you're listening to a voice channel on Fleetnet Zone 2.
NAC also behaves much like CTCSS or DCS as far as scanners go - if you set your scanner to receive a signal with NAC 293, then if I set my radio up on that same frequency to send NAC 050, you're not going to pick me up. So, in that regard, it's just as useful to know NAC as it is to know CTCSS/DCS.