Thanks all! The "spark" for my question came from building survival kits with our Scouts. Matches, lighters, ferro rods, mag sticks, magnifying glasses, steele wool .... we teach them all and tell them to always try to carry at least 2 or 3 methods on them.(After thoroughly teaching them fire building skills first, of course, so they're ready for fire lighting.) We want to teach them the easiest, most reliable method first. Once we've covered the 2 or 3 components they carry in their kits, what would you move onto next?
We used to start by teaching how to use matches and the steel wool/battery method. They're relatively easy for the inexperienced to figure out and use. From there we moved onto the magnifying glass and the ferro-rod (typically the BSA hotspark). Everyone would get a chance to try out everything. After that we would sometimes demonstrate making fire with potassium permanganate and glycerin (this was done more because it's a neat thing to see, rather than as a viable method for scouts). That pretty much covered one meeting when combined with teaching the safety aspects of it.
The next meeting would cover traditional fire starting methods. Bow drill, hand drill, hand drill with thumb loops, and flint and steel. From there the boys would try making smoke with both the bow drill and the hand drill. This meeting was also used to go over the importance of building a fire properly from tinder, to kindling, to fuel (as well as reinforcing the safety aspects). Sometimes this meeting would end with one of the leaders (or one of the older boys) making a fire using one of the traditional methods, and then letting the boys roast up some marshmallows over it.
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