You have two problems.
The first is a safety feature. Because so many people have gotten burned from taking off radiator caps from hot engines radiator caps require two seperate turns to take them off. The first turn releases the pressure but holds the cap in place. The second turn, achieved by pressing hard down on the cap while turning, removes the cap. There is a little stop (there for safety) that must be conquered by depressing the cap in order to turn the cap enough to remove it. If it doesn't depress and turn easily then your only choice is brute force. Find a big, strong friend or neighbor and offer him beer and cookies if he can get it off.
Your second problem is most likely the gunk that has accumulated under the cap. Once removed, take the cap inside and give it a good cleaning in hot soapy water. Once cleaned you should find that the cap can be put back on and removed fairly easily.
The steps should be (1.) turn the cap 1/4 turn counterclockwise (2.) depress and turn the cap another 1/4 turn (3.) lift the cap. Keeping your cap (and your radiator) clean should avoid this problem in the future.