I suspect that gun had a similar problem to one I saw years ago. The hammer was so misaligned with the nipple, that the skirt actually rubbed against the nipple on the downstroke, preventing a sufficient blow, most of the time, from firing the cap. All you would need was a cap like the one my father found, where some of the compound was spilled down the inside edge of the cap, and you would creat a match-striking situation, where remove the cap, with any kind of friction could set off the cap mixture, now transferred to the side of the nipple. In our case, the cap blew outward, from Dad's revolver, and barely missed us when he fired the defective cap. In your friend's case, the compound got on the nipple, and lifting the defective cap off with a knife scraped the compound and ignited it.
As I said above, I now inspect all the caps at one time when they are loaded in the capper. I remove any that don't look right,( like the rest of the caps) and throw them away. Its just not worth it fiddling with them. I only find one or two defective caps per thousand, but its stil worth while taking a look just for the peace of mind.