how best to optimize steam with a SSD?

[Homer Simpson]

my current config consists of a crucial m4 128 for OS and two WD Black 1TB drives (raid0). i use the ssd for windows and apps. steam, origin and impulse are all on the raid array. im wanting to add a 2nd SSD for games. my question is, should i leave steam, et al where it is and use steam mover to move my commonly used stuff to the ssd or reinstall steam to the ssd and use steam mover to move off the less commonly used games? i guess im wondering if the steammover junction trick adds any overhead. for example, if i left it as is and used steam mover to put my most used stuff to the ssd, when i "call" on the game, does it first go out to the slower spindle drives then redirect to the ssd (and thus add latency) or does it just know to go straight to the ssd? or is the impact so miniscule its not noticeable?