Much of the off-piste skiing in the East is trails. Even if you're skiing slides in the Daks or ravines on Washington, you'll need to ski trails to get there. It's a whole 'nother skill set, and can be pretty fun in it's own right.
There's lots of skiing in VT, but I'm not familiar with it. I do know the High Peaks, which is a great place to start.
First thing I'd do is rent a setup. It will run about $50 a day, but since a new AT setup is $1500 or more, it's a cheap way to find what you like. Most places will put rental fees towards a setup if you buy from them.
I'd start at the Mountaineer - rent a setup, and try some of the rolling sections of the JackRabbit XC trail. Just a morning will probably get you familiar with the basic operation of the AT gear, and trail skiing.
After the JR, there are a bunch of classic trails. The big ones are Avalanche Pass, Wright Peak, and Marcy. Either of the first two would be great to jump on after you feel good on the JackRabbit.
Next up - slides. There are plenty, but in general require some Avy skills. The ADK ski festival is a great place to learn about them.