Hooboy. Ok, first, one has to consider the wisdom of putting themselves in a position where using a booster for a really slow powder is necessary in the first place. My advice is don't deliberately buy a bunch of slow powder just for the purpose of duplexing it unless you're trying to do something really special like shoot cast bullets accurately WAY past the normal accepted velocity constraints of bare lead....and already know what to buy and how to use it.
If you find yourself just wanting to experiment, work with buffers first, it will teach you a lot, particularly about how to respect more dangerous than normal things in handloading.
On to the philosophy. So you have some WCC872, 867, or similar. You've used in in your favorite cast bullet slinger (say, .30-'06) with cast bullets and just can't make it burn well. You've worked with a particular lot of it enough to know how much you can use with your particular combination of components. If you can fill the case with it and not encounter dangerous pressures or weird ignition, yet it still won't burn cleanly or give consistent velocities, then it's time to consider a "kicker" or "booster" charge to enhance ignition. Think of a booster charge as merely adding more spark to and extending the primer's heat. The way to use it is add about two or three grains of booster on top of the primer and subtract the same volume from a 100% load of the slow-for-cartridge powder. This all assumes that the grains of the booster and main charge are compatible shapes and sizes so they won't intermix much. Go shooting. Make observations and compare them to those of the 100% un-boostered load. If it seems prudent, add another grain of booster and repeat. The max I would ever go with a booster charge is about 10%, though some go 15% or so with certain booster/powder combinations. The idea is to make a powder like Reloder 50 burn more like Varget or 4831, and use your booster/main charge combo in different cartridges that would enjoy a powder in the medium-slow burn rate.
Sooooo, what to use for booster with smoldery double or triple-based cannon powder? A fast-burning, single-base, extruded rifle propellant. I'll leave it at that.