Move controls for PAIN:
first of all, there is a new option in the main menu "Painmotion". Apparently those are Move specific challenges, but it says I didn't download it from the score (is it that new DLC?)
Not all existing modes[maps] (I didn't buy any DLC) support Move. If they do, they are labeled accordingly (with the exception of Painlabs) as they are a new selection in the menu: Paindemonium + Fun with explosives (and all sub modes) for singleplayer and Horse for local multiplayer. The Move controller doesn't work online.
Before loading a map you have to calibrate the controller (at the end you have to smack a monkey on the ass).
Then you will see a radical change: there is no catapult! Instead when holding T, you hold your character with a white little hand in midair. Releasing T will also release your character.
You do a somewhat irl throwing motion to throw the character ingame and it actually works quite well (the faster your do the motion, the harder you throw). For me, this is a better Move implementation than Hustle King or HVB as it's not just a remapping of the DS3 controls but you actually do a 1:1 motion which is kinda fun.
However, PAIN kinda depends on the fixed catapult as you can tweak the settings to target something specific and so on, so... it's more to just mess around I guess (maybe the Move challenges are different).
I made a little replay:
http://www.youtube.com/watch?v=QEJlDs604fQ
though it starts recording after you release so you can't see the hand movement, but you can see that there is no catapult and I believe you can't "ooch" so strong with only one motion (normally pressing the digital pad several times)
other controls:
Move button = top view
Move button + T = resets character
X = turn left before throwing, O = turn right
Start= pause menu
select = reset map
after releasing the character:
shake move = fill super ooch
hold T and move the Move controller to ooch your character in that direction
grab things with the face buttons
Triangle after resetting the character (and not holding T) = activate replay mode
Apparently, with Move you can't do the stunts while in the air, this will gimp your combos I guess.
oh and the Move sphere glows in red.