GS back/shoulders/biceps has a good shoulder section. I really feel the burn in that one (especially with the addition of the band moves).
More than any particular shoulder workout, it's also important to give any muscle recovery time to grow. The shoulder is worked not only when doing specific shoulder exercises, but also when working chest and, to a lesser extent, back, so make sure that you leave good recovery time between chest and shoulder workouts, for example. If I do a 3-way split routine like GS, I find that my sholders get the best recovery and chance to repair and grow if I put the two upper body workouts as far appart as possible, so I will do chest/triceps on Monday, Legs on Wednesday, and Back/shoulders/biceps on Friday. Putting the leg workout in between the two upper body workouts gives me that extra time, and is also kinder to my shoulders.
On another note, make sure that whatever workout you choose, it includes work for the rear delts and side delts. The rear delts are often "forgotten" in workouts (Cathe doesn't hit those in her earlier workouts), and developing the side delts gives width to the shoudler area.
I personally often omit isolated front delt work, especially when doing an "all upper body workout," because chest work hits that area as well, the front delt can easilty be overworked because it's used in so many daily activities, and muscle imbalance between front delts (strong and tight) and rear delts (weak and stretched) can cause posture problems (rounding forward of shoulders, that you can see in some body builders, like that John Basdow guy on TV) and increase risk of shoulder impingement.
For the isolated front delt raises in PUB, for example, I sub an overhead press (but I do it at the beginning of the shoulder exercises, before the rear and side raises, so I kind of "do my own thing" in this section while working out with Cathe and the crew).
For "non-Cathe" workout, P90X has some excellent shoulder exercises. I just did "Shoulders and Arms" the other day. A great workout!