My understanding is that you try different tubes in one component. Such a Sovtek, Western Electric, etc. seeking the best sound or the individual sound qualities that each tube brings. Or maybe rock sounds better with one and classical with another. Contact mofimadness as he has drawers of tubes that he uses. I guess it is kind of like a chef using different spices and seasonings to individualize each palate. I would like to do it but only have one set of tubes so far.
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Theo basically has it right.
It is basically just substituting different tubes from the stock tubes that came with the unit. Typically this yields different sonic results depending on the tubes. Usually better results, but sometimes worse. (Typically, but not always, NOS (New Old Stock) tubes will yield better results than current production tubes, since they were manufactured during the peak days of tube use (i.e. in the '50s and '60s). And, as you can imagine, NOS tubes tend to be much more expensive than stock tubes, (and get only more expensive with time, since they are slowly but surely getting more rare, as the supply is used up).
To get an idea of the sonic differences between tubes, check out Joe's Tube Lore @ Audio Asylum, (to which I have provided a link below).
Joe's Tube Lore @ Audio Asylum
I hope that helps!
I also agree that you should read, (and reread) Joe's Tube Lore at the link provided. It's pretty much the bible for the different ways tubes sound.
Just remember that the actual component that each tube is used in, makes a BIG difference. I have never found the same tube(s) sound the same in different gear.
I really like the Amperex USN-CEP 6922 tubes in my DAC, but they suck in my phono preamp. Each circuit and the way it "uses" each tube is completely different.
While others have clearly defined tube rolling, I would like to add the benefit of NOS tubes. The difference in sound quality you will experience is astounding. Unfortunately this may be somewhat design dependant and not 100%. I would recomend numerous specific inquiries before spending hard earned cash'