Re: Best modeler to plug directly into PA
For heavy stuff, the stock models are pretty good - especially the Spinal Puppet(Mesa-like) and Modern Hi-Gain(Soldano X88R). The Jazz Clean(JC120) model is my choice for clean stuff.
I spent the extra $50 and got the Metal Shop pack. The stuff in there is really useful; the Big Bottom(triple rec with a sub cab) and Criminal(5150) models are very popular, as is the Bomber Uber(Bogner Uberschall). This also nets you three more high-gain Marshall models, if that's the flavor you prefer.
The "Boost+EQ" stomp is worth playing with. I use it for boosting my dirty patches and sending my cleans into mild to moderately crunchy territory; switching up your EQ without changing patches can be really helpful in some situations - there's a momentary silence when you change patches, but not when you switch an effect on or off.
It's worth getting comfortable with both Gearbox and Line6 Edit, though Edit offers a few important things that Gearbox doesn't, namely the ability to assign your expression pedal to tweak one effect's parameters, which is usually set to work with the Bender stomp, and to set the "amp" button to turn the compressor on and off, rather than toggle the amp on/off.
Also, I strongly recommend running the Pod through studio monitors, good headphones, a PA, or home stereo. PC speakers are not your friend, and guitar amps will probably do things you don't like to the sound, assuming you'd like your home/practice sound to be as close as possible to what you're putting through the PA. Also, remember to compensate for the infamous Fletcher-Munson effect when building patches for live use - you're probably going to need to boost your mids a little for gigs.
...that was a fair bit of babble. Is there anything in particular you'd like pointers on?