I'm no grammarian by any stretch of the imagination, but the way I see it is that "a" or "an" is defined by the first abbreviated letter. All vowels used as the first letter of an acronym will be preceded by an "an".
Some consonants begin with a consonant sound, so they will be preceded by an "a", but some consonants begin with a vowel sound instead. Those are the ones that may cause confusion. I'll show you what I mean below.
F = ef (This is the first consonant of the alphabet which, when used as the first letter of an acronym - ie. FCC - would call for the use of "an" because it begins with a vowel sound.)
H = heych, eych (Depending on your regional usage, this will be either "a" or "an".)
L, M, N = el, em, en (Same rule as F.)
R = ar (Begins with an a sound, therefore same rule as the e-sounding F, L, M and N.)
S, X = es, ex (Same as F, L, M and N.)
I hope that helps.