This is one of those times that truth and Hollywood just don't match up. It's not just TV shows either, popular survival forums tout this as being an infallible fire starter. I doubt most of the people who preach its virtues have every actually tried to make a fire with it.
The fact is, Potassium Permanganate and Glycerin will make a great fire. What people do not tell you is that for the chemical reaction to happen the ambient temperature needs to be around room temperature (70 degrees) or higher. What they also do not tell you is that you still need dry tinder and everything else normally necessary to make a fire. Oh, and another thing, they are not commonly found in first aid kits!
Check this out:
Potassium Permanganate is a fairly common chemical. You can purchase it in the water treatment area of hardware and pool supply stores. It is useful for a lot of things. Potassium Permanganate is an antiseptic. In high concentrations it can be used to kill foot fungus and generally disinfect stuff. To make a disinfectant with it, mix it with water until the water is dark purple. At these concentrations it is toxic, so take care.
It can also be used to disinfect water. Notice I said disinfect, not purify. It will kill most bacteria, but pollutants and poisons may still be in the water. To disinfect water mix in just enough Potassium Permanganate to give it a light purple color. Let the mixture sit for an hour or two before you drink it. It should be noted that this is not for long term use. I've also read not to use it if you are pregnant. Potassium Permanganate also stains. A little spread over snow will appear bright purple and can be used to mark your way.
Glycerin can be found in drug, craft, and baking stores. It has many, many uses. However, it doesn't have many uses for an outdoorsman. It can be used as a suppository to help with constipation. It can also be used as a lubricant. Which I guess is why it helps with constipation!
Neither of these are stocked in any first aid kit I've ever seen. You will not find these chemicals out in the wild. While Potassium Permanganate has some valuable traits, there are better alternatives. I see no reason to carry either with you in the woods. Their main purpose, making fire, only works when it is warm outside! Do yourself a favor, instead of packing these two chemicals with you, just throw in an extra box of matches.
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