I'll just bring this up as a very small possibility, and maybe it is only theoretical, since you said you first encountered this when the amp was "working".
But "working" could mean one of two things: 1: You were actually playing thru the amp, touched utterly nothing, and in between playing two chords or two notes, suddenly smoke/smell appeared. 2: It could also mean the amp was working fine, you decided to look at your 6V6 tubes, turned power off, pulled the tubes, then put them back in, even putting them back in the same sockets they came out of. Nothing changed, right?
But I have seen this happen when the output tube sockets are very worn and one (or, I suppose both) of the output tubes has been inserted one pin off because the keyway in one or the other sockets no longer uniquely locates the 6V6 in its socket. I could hardly believe it when I saw it, because I saw it in a school amp I was fixing, and I can't imagine the 6V6 were pulled out more than once or twice in the entire life of the amp (an 80's Deluxe Reverb II) So how could the 6V6 sockets be so worn that you could put the tube in one or more pins off?
Well, they were, whether I believed it or not. Did I look to see whether the 6V6 tubes were installed correctly? No, I just placed the tube over the socket and spun it until (I thought) the key on the base found the notch and the tube dropped into index, like I've done 40,000 times over 40+ years of working on amps. The key on the base locates them so they can only be installed one way right? Wrong! I was able to install the 6V6's 3 or 4 different ways/rotations. I could hardly believe it. It could *also* be a situation where the socket is slightly worn and we go to install a JJ 6V6 or some other "modern" brand of 6V6 and center keyed post is microscopically smaller than a 1960's RCA/GE 6V6 for reasons we can only speculate about.
When Doug said "I have seen that happen when the very large voltage on the plates of the power tubes (pin 3) arcs across the tube sockets to pin 2....That is almost a pure path to ground"
That is what will happen should the tube be installed rotated one pin off. And obviously, if the center key goodie is broken off and the tube is reused anyway, it would be easy as pie to get the tube rotated one or more pins off.
So as I said, it's a really long shot, but it is less of a long shot if you never even suspect it might be a possibility.
It is also true that this is the situation where you are really happy that you have the "synthetic" center tap versus the "actual" center tap on the 6.3 winding.