I always assumed it to be formed primarily out of the government "elite". The President, his Secret Service, top CIA agents, as well as high-ranking military commanders and generals. I would not say that the actual armed forces were part of this in any way, just the ultimate powers in the American government. And you're right in that the Brotherhood of Steel was just founded by a detachment of soldiers led by Maxson who travelled to the Mariposa base.
What you do have to understand however, is that all of these powerful government types do have some influence over the country's defenses. They may not all fight in war, but they do probably have access to all the nuclear launch silos, still-functioning orbital satellites, and all sorts of other military tech.
That makes a lot of since, but there are so many Enclave soldiers (and they have arounf 10 bases (There is a map in FO2 that has dots showing Enclave base locations, 1 being in California (Navarro), 1 in DC (RavenRock), and 1 off the coast of California (Oil Tanker thingy).
There must have been a tons (Nearly 10,000) of Enclave at the start of the war if there are 10 Enclave bases (If they hold 1000 people each). There must have been more than just the "Important Elite" of the USA.