I assume you have an automatic transmission?
On a 3.0l, no, the valve timing is set by crank gear and cam gear connected by a timing chain located inside the timing cover, so behind crank pulley.
Turning crank or removing pulley will not effect anything inside the timing cover.
If you have removed the CPS(cam position sensor) and synchro housing, then yes turning the crank will effect its timing, put it back in and then use breaker bar and bump starter motor.
Yes it can "fall off" but just put it back on, it can't "fly off".
The crank turns clockwise, so put the breaker bar on the drivers side against the ground, so ground will stop bolt from spinning clockwise, crank turns bolt doesn't so bolt unscrews, counter-clockwise.
One important thing.................MAKE SURE SPARK is disabled, don't want engine to start
But all in all you will probably have to remove the radiator since you will need a puller to get the pulley off in any case