First, I would suggest taking a trip to an Indian or ethnic market. Don't be shy. Pick up packages and smell them. Ask the people who work there what they use them for. Write down the names of the unfamiliar and look it up when you go home.
And then start trying things out. One of the lasting benefits that I've found to doing a kitchari cleanse is that it's helped me learn more about the characteristics of different spices. The neutral canvas of the rice and mung beans are excellent for experimenting with spices. That's how I learned that I love ginger...but I hate Garam Masala (at least in large quantities!).
For example, this evening, I didn't want to heat up the apartment with the oven, and yet I didn't want plain boiled yams. I took my yams and diced them and sauteed them in ghee, madras curry, a little chilli powder and a little ginger before simmering. When they were cooked through, I added coconut milk and ended up with a divine (if a little Kapha agravating) side dish.
What do you do when you add too much spice to something? If you have coconut milk on hand, it can definitely add flavor and dilute the spiciness. If you don't, plain yogurt is also a great compliment to super spicy foods.