EC is *awesome*! i heartily recommend that you give it a try. i think the best way to do it if your baby is signaling is to just jump right in and try it! keep her in something that's easy to get off, and preferably without a cover. and keep a receptacle of some sort close at hand (little potty, bucket, bowl, whatever you've got handy). then when you notice her signaling, just whip off the diaper and hold her over the receptacle - up against your chest with your hands behind her knees - and say "psssssss". try to take some deep relaxing breaths so she can follow your lead and relax herself enough to pee. if you notice that she's starting to pee while wearing a diaper (which is why coverless is preferable) make the "pssssss" sound then too, so she starts to connect your cue with the feeling of releasing.
probably the easiest ones to catch are immediately upon waking from night or nap, since they haven't gone in a while and most babies pee then.
it can also be helpful, especially if your baby doesn't always cue, to keep a little log for a while of the times that baby nurses, sleeps, and pees. sometimes you don't realize what an obvious pattern your child is in until you keep track, and then you see that s/he always goes at xx o'clock, or 30 minutes after nursing, or whatever. so that can be really helpful.
i think the most important thing about it is to relax and not try to catch everything. focus on the communication it fosters between you and your little one - going through fewer diapers is just a bonus