I am glad to say that the Pronto is now able to power on/off my S7000 DVD. Thanks everyone for your help.

I tried re-learning with a momentary press to no avail. I also tried deleting and recreating the on/off buttons. The fix was to delete the DVD template I was using and create a new one.

While this is somewhat strange behavior, having to use a brute force method of deleting the entire template, I can honestly say that the Pronto is by far the best remote I have used and a welcome addition to my home theater. Can't wait for the software!