...In software they're only enabling one GPU for compute, and one for graphics, and it would be trivial to change this if so.
This assumption is incorrect. The statement made was that by default Mavericks uses one GPU to physically control displays and the other to process memory intensive computations taking some of the burden off the CPU.
Adobe Photoshop CC and Adobe Premiere CC have taken advantage of OpenCL to assign specific computational tasks to the GPU, but have not yet implemented both GPUs in the process.
http://community.amd.com/community/amd-blogs/amd/blog/2014/01/30/new-adobe-photoshop-cc-blockbuster-features-scream-on-amd-graphics
The software option that some manufacturers have already taken advantage of is to engage the power of both GPUs in aiding the CPU by processing specific computations through OpenCL. Apple's Final Cut Pro and Mari 3D paint software have enabled the power of both GPUs with open CL.
http://arstechnica.com/apple/2014/01/two-steps-forward-a-review-of-the-2013-mac-pro/4/
"OpenCL is currently used in the realtime rendering. We need to render the screen a few times each frame to find out what texture tiles are visible, we then need to process that image to work out the set of unique tiles. The images we pre-render can be very large (up to 4k x 4k) so that is a huge amount of pixels to process in real time.
We use OpenCL on OS X to perform this processing. This processing has the option of working on the second GPU. This is set in the OpenCL preferences tab. We are working on offloading more of the processing onto OpenCL and the second GPU." - Mari product manager, Jack Greasly