Can I zap myself biasing my tube amp??

If you are worried about those close encounters of the electical kind, then truck on down to your electronics store and get a CG tuning stick. They are red plastic and if you touch it to high voltage you will not get shocked. They are used for tuning transmitter plate voltages. They're about $2.00.
But since most amps are designed so that you can bias them without any danger of getting shocked you really don't need one.
I use mine to pry open remote controls for cleaning. They don't leave marks on the plastic like screwdrivers will.

Get some help. If you have never done this before, it can be very dangerous. Just the fact that you are considering rubber boots tells me that you may be unaware of the precautions needed. The place you want the insulation is on your hands. You may not get a second chance if you make a mistake. A tenth of an amp is all the current needed to be fatal.

Only if you do it orally.

All the way to a wooden Box.

BTW don't think that having an amp off is protection against sticking your mits in the wrong place. If the capacitors are not discharged you can fry as easily as if the thing was plugged in as they are energy storage devices and that energy remains stored waiting for your knock on the door even with the amp off. That said there are thousands upon thousands of tube amps in service and they are regularly biased by their users without incident. Might I suggest calling VTL to get the manual if you do not already have it. Review it thoroughly it will also tell you which scale to use on your multi-meter and the correct bias voltage or amperage. I would imagine that VTL would also be more than helpful if you do not clearly understand any of the procedures outlined in the manual.