The best way to think of Hunt groups would be like a conventional ring-group. It is a dialable number that you can assign members. There is some flexability on ringing but typically it would be simultaneaous.
If hunt group is busy or off hours it can route elswhere.
You can make a hunt group busy by dialing *80 + huntgroup
Work groups are more ACD orientated. You need a license for the agents to have the agent communicator. (you don't need a license to have agents be a part of the WG though)
You get additional options by way of queueing, reporting, agents logging in or out, and supervisor options.

I sent you a PM if you would like to discuss in more detail a setup design specific to your needs.

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