OK, here's an explanation as to why there are two shuttles on pads this time, but not any other time (my own words).
In a typical mission (which, post-Columbia, means one that goes to the ISS), in the event that a shuttle is damaged such that it can make it to the ISS, but cannot land, the crew recovery plan involves transferring as much supplies (fuel, air, food, water, clothing etc.) from the damaged shuttle to the ISS and then closing the hatches with all crew onboard the ISS. Special cables and software is installed on the shuttle side to allow NASA controllers to attempt a remote-controlled landing (or, if that is not possible, a safe de-orbit). NASA then prepare a recovery mission using a second shuttle to rescue the crew from the ISS. The combined shuttle+ISS can (by rationing) maintain a crew of ten (or thirteen) for approximately 45 days, which is sufficient to prepare and launch a CSCS rescue shuttle. See also
Wikipedia:STS-3xx
With Hubble, no such 'safe haven' option exists. Due to fuel contraints the ISS is out of range of the shuttle, and the crew must manage on shuttle resources alone (which, for obvious reasons, are significantly less than those available onboard ISS). For this reason, there is no time to prepare a second shuttle and it must be ready to go. This is now even more important given the debris problems of recent times. See also
Wikipedia:STS-400
Of course, pre-Columbia, none of this would have happened, but now NASA appreciates just how fragile the shuttle wings are, they have to take such precautions to avoid another crew loss. In any event, if the shuttle doesn't make it into a sustainable orbit, no rescue is possible.
PS - my first post was incorrect. This will be the only non-ISS mission in the manifest. The additional mission being planned is another mission to deliver scientific hardware to ISS.