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Do keep in mind that in addition to being at peace you also must not have a truce with the current Emperor as well, so maybe that's what's preventing it for you?
But since you just want to get it for the achievment, check the in-game achievment tracker. If I remember correctly in one of the recent patches it was changed so that you need only be a member of the Protestant League, not the leader.
No more applicable to your game, but well...
Just set up a pause for the event of league creation
First one to join catho league will be Emperor (usually Austria) and this will set the game to pause.
Join immediatly protestant side (you will be alone, so leader...) and declare while on pause.
You will have of course to fight and win against Emperor + allies