When I started in design, my knowledge of fonts (or typefaces, if you prefer) didn’t extend much further than Times and Arial.
Now, my work is primarily all about fonts in terms of choosing the right ones and using them properly.
But I ran across something the other day that I wish I had when I started. It’s a nice PDF of font combinations that work well together, especially in subhead/body copy usage.
It is just one person’s opinion, but if you’re starting out and totally lost, one person’s opinion is a big help.
From the list on the BonFX site, I favor the Myriad/Minion combo. I also use Myriad/Garamond a lot. Like any designer, I actually use a number of combos, but those two work really well for the types of projects I do.