Hi Adam. Andrew has a project file download that is helpful in wrapping your head around Sections Pro. You can check it out here: http://sectionspro.bigwhiteduck.com/posts/?permalink=learn-sections-demo-site
This is useful in any case BUT I have to apologize in not reading your question carefully. I just looked at your images and not the link and thought you were asking about changing the individual grid boxes on hover. That is done very easily with Sections Pro.
However, I’m not at my RW computer to see if changing the full background on hover of a single grid item is possible (you know, the actual thing you asked, and did so clearly if I read carefully). Not saying it isn’t possible, just not sure off the top of my head.
In the meantime, maybe @tav could say if this is doable? EDIT: Andrew is away this week unfortunately.