Some researchers of cat behavior believe that cats show what is known as "relative dominance," i.e. the order of dominance among a group of cats can change depending on the situation, the location, the time of day, etc.
For instance, you can have a cat who is dominant at feeding time first thing in the morning, then retires for a nap or whatever, allowing a second cat to be the dominant one for playtime or feeding. Cats who are lower on the totem pole will sometimes stake a claim to a particular chair and behave dominantly toward other cats who want to sit in the chair. Or one cat might dominate a windowsill during the morning when it's sunny, and a different cat might dominate the same location later in the day.
IME, the one who most often demands to be fed first is the one who's the most dominant overall. The pecking order isn't always clearcut, however. I personally think one of the alluring things about cats is that they don't fit nearly into "cat"egories.