"throbbinut,
What about amps that are cathode biased? Any 'coating' is going to get blasted to hell by a major voltage swing across the plates."
Yep, when a cathode biased amp is turned on, there is a period of time when the amp is running without correct bias. If the cathode bypass cap is insanely large, it is an even longer period. But, I don't think it's that big a deal. It's not like it only takes once or anything. It's an accumulated effect. My 1979 Fender Musicmaster Bass amp is cathode biased, and it has no standby switch. So it gets the double whammy on each power up. And even so, it still has the original Fender tube set in it and works great.
As for power down method, it probably doesn't make a damn bit of difference. If I'm about to work on the amp, I just kill AC and leave Standby on to drain the filter caps. If I'm about to put the amp in the closet for a year, I kill standby and then kill AC, so the filter caps will retain a charge for a little while. If electrolytics are stored for long periods of time, they "un-form", and have to be re-formed before use. My little trick probably doesn't do any good in the scheme of things.
As for cathode poisoning, I heard about it on Rec.Audio.Tubes. I don't dismiss it, but it is probably not a big deal either.
Here is one thing I know, when you open a switch that is feeding an inductive load, you get a surge and usually an arc at the switch. In Fender Bassman amps, the standby switch feeds directly into the output transformer primary center tap, and filter choke. Not having the switch go directly into a capacitor prevents a surge when the Standby switch is turned on. But I think the pop that is heard when standby is turned off is due to the inductive spike when the switch is opened. For this reason, I leave the standby switch "on" when I power down, to protect the switch.
Just as an aside, tubes last a hell of a lot longer than people think they do. But I still try and treat them nice.
Chris