In addition to cross division matches, I would say that we should go for cross region matches as well. While the Americas and Europe have similar metagames, East Asia has a bit of uniqueness that could bring a nice spark to the channel (however, how you go about contacting them is past me.)
Of course, a snazzy introduction alongside unprecedented quality are also needed. With the amount of manpower available I'm sure we can get some amazing videos up whether it be on the SmogonU channel or something completely new as long as this project is kept organized.
Just a suggestion with how you should go about this - take your time. All the excitement and willingness to help can make it seem like the sooner this is done, the better. While there is truth to this, make sure to remember quality > quantity, especially with the first couple videos so that a high standard is established.
If there is anything I can do to help, let me know. Best of luck!