From a PvE standpoint, man... I wouldn't worry about the totems. I'll tell you what I do, though.

Water shield, of course. Then just spam lightning bolts or chain lightnings. You basically will drop mobs super fast. Every now and then, if you're going to stick around a single spot (while maybe targeting multiple groups of guys) drop down 5x Mana spring totems (Since they now stack!).

If I am in a spot where I'm worried about a particular elite fight, or something, I set up my totems like this:

Air: I generally will drop 5 Grounding totems (For any monsters that may use spells, or if you may get ganked by someone). I don't melee, so these tend to be the best thing for me to use most of the time. I have a second set that I soemtimes drop, using the Alt key of the regular Air totem key, that will throw down a windfury totem and such, but I rarely melee.

Earth: A stoneskin totem, a temor totem and three stoneclaw totems. If you pull with a lightning bolt instead of a chain lightning, the stoneclaws provide some nice distractions while you take out a few monsters. This one you can play around with a lot, if you need to. For the alt of this key, I have a rotation of Earthbind totems.

Water: Like I mentioned before, mana mana mana. I do 5x Mana totems pretty much all of the time. If there's a fight where I'm worried about healing (and not mana), I'll generally do 4x Healing and 1x Mana. Again, these share the same action bar slot, but one is triggered with the addition of the Alt key.

Fire: I dunno... This comes down to personal choice. There's lots of cases were 5x Searing or 5x Magma can be quite handy. I hate killing monsters with totems, though, since you can't loot them, however, so generally I don't even bother. If it's an elite, I'll maybe pull with LB and then drop 5x Fire Nova totems to soften up the monster a bit, then follow it up by 5x Searing. Searing does more damage, but if you have lots of guys around you, 5x magma will do more combined damage.

Hope that helps. It really all comes down to play style.

If you want specific macro information for shamans, the wiki has some pretty good write-ups.

A-Team