Shouldn't this be in Gamethought?
Well, the first step is the pinky. If you don't get VERY comfy using the pinky, you're screwed. You basically have to be able to hit the blue, with your pinky, like any other fret with your other fingers. It's awkward at first as we don't really use our pinky so regularly normally. It's kinda like getting used to it on a keyboard, it just takes time.
Next step, IMO, is to stop trying to hit the notes coming at you and start playing the song. What I mean by that is, you have to listen to the song and the rhythm first, play the notes second; basically, play the music not the game. This is what I was taught in music class in high school and it works very well for the game as the game's difficulty is hard enough and the basis of the game is really the music more than the game aspect (this is why I love it so much). You'll find that the notes come from music, not the other way around. So, you learn what the song - or that particular part of the song- sounds like THEN you play the notes relating to the music. In harder songs, you really can't see all of the notes, it's freakin' impossible. So you play the song rather than hitting the right fret at the right time, which is paying the game. This is especially important when you're playing on Expert.
After than, it's matter of fine-tuning your ability to move up and down the neck of the guitar to play the orange fret (more in Expert than Hard) and not losing the positioning of your hand on the frets when doing so and/or playing chords. Use your Star Power to get you through the hard solos. This wasn't a problem on Easy or Medium but you'll soon find it's necessary to get through some of the harder songs, particularly on Expert (later you'll have to strategically use the Star Power to get higher star ratings, but that's another discussion).
And, of course, it's all about practice, practice, practice :-)
I was there on that fateful day, were you?