The question of CDR is an interesting one as it's always useful, it's just a matter of whether it's more useful than another item/effect you can get sooner.
Most of the time it's a matter of damage + resource vs. CDR. It's always better to have your abilities up as often as possible no matter who you're playing but if your spells do nothing then having more of them usually won't matter, or if you're oom then it doesn't matter either way.
CDR will, obviously, scale best with higher cooldown spells. And in that case it's usually a matter of who you're playing. Udyr, for example, will not use CDR as much as, say, Leona because all of his spells are low cooldown normally and you'll burn through mana really quickly if you're spamming.
Okay, I'm getting a bit too broad on this so I'll sum it up with how I determine if I need CDR: play the champion first and if you every have an instance where you keep needing an ability and can't then build more CDR than you have been. As patterns go, aggressive champion will use CDR more than defensive champions, because you're defining the tempo. There are also specific cases where a champion revolves around an aspect that's dependent on CDR. Nasus, for example, uses early CDR very well because that means more Q stacks. I always rush a kindlegem or glacial shroud ASAP on him depending on who I'm against. Supports also use CDR very well because they don't need to worry about damage.
Ones who almost avoid CDR in favor of other stats are marksmen and some assasins. Where their one-salvo burst and/or autoattacks are more important.