As long as you're getting plenty of E with your multi, then you don't really need to be concerned about taking it immediately post-workout. (Since it's fat soluble, it stays around longer than the water soluble vitamins.)
You do want to get vitamin C and the B's with your post workout shake, though. (Vitamin C to counteract the free-radicals produced by intense exercise, to help lower cortisol like T.R. said, and for a host of other reasons. The B's are important for metabolism and protein utilization as well.)
Try to make sure that your post-workout B-&-C pill is a capsule, instead of a tablet, so that it dissolves as quickly as possible and can get into your system at the same time as your whey, dextrose, or whatever else you have in your shake.
I personally use Twinlab's "Stress B-Complex Caps". The label states to take 2 caps, but one is just fine, and will still provide:
C - 500mg
Thiamin - 25mg
B2 - 25mg
Niacin - 50mg
B6 - 25mg
Folic Acide - 200mcg
B12 - 125mcg
Biotin - 50mcg
Pantothenic Acid - 125 mcg