Headshots are important and all, even more so on PC than what I'm used to, but I honestly think that if you're trying too hard to get headshots, you're gonna screw yourself. Whether it's from taking too long to line up a shot, taking the shot and missing, or both, it doesn't matter. Sometimes, it's better to guarantee that you'll hit them, than it is to hit them hard.
Another thing to do is mainly be relaxed. Forgot to mention that xD
Yeah, I agree, if you try too hard for those and it's bound to get you screwed however, it's better to look at the head angle because let's say an Assault rifle's first bullet on the head will instantly lower the enemies health instantly so giving you a higher opportunity to kill the person.
It takes practice no doubt, but it's something all the big leagues out there do.