Good Eats should come out on DVD. Seriously.
WRT herbs/spices, in addition to what Jdvn1 said, one thing to keep in mind when cooking with spices is that dried spices are quite a bit stronger than fresh ones. When following a recipe, make sure to note if it calls for dried or fresh spices. You can substitute one for the other in about a 1:3 ratio of dried to fresh - that is, if a recipe calls for a tablespoon of fresh oregano, a dried equivalent is about one teaspoon.
However, season to taste. While some spices go better with some things than others, really your best bet is too experiment. For example, I've found that with a simple cheese and potato soup, a few drops of tobasco sauce adds a nice subtlety to it. Cocoa is a must for a serious chili, even though you wouldn't really think it. Oregano and parsley tend to go with everything, and are better fresh, but that's just my opinion. Experiment and don't worry if something doesn't taste completely right, just make a note and try something different next time. Most of all, have fun!