Rudder's right on with the steps.
Image A = person/people you want to add
Image B = group to be added to
1) Open A, double click 'background' in layers palette to make it a layer
2) Add layer mask to 'layer 1', use paint brush/select&fill/magic wand/select color range/whatever to mask everything but your person
3) Open B, copy 'layer 1' from Image A to Image B (right click on the layer and select "Duplicate...")
4) scale/position layer 1 to the appropriate position
5) continue masking layer 1 wherever your subject should be "behind" things in the group image
Step 2 can be very challenging depending on the subject. Hair is typically especially difficult. There are many products that can get you good starts on masks (like Vertus that rudder mentions) but I've never seen any product do a perfect job.
If the backgrounds permit, sometimes you can bring more than just the person - some sky, perhaps, then feather the sky or whatever into your destination sky.
Those steps don't include things like color correction if the lighting or environment aren't similar from A to B. If your subject is, say, in a library in between stacks and your destination is a sunny soccer game, you can expect to have somewhere between a near-impossible and impossible time getting the "transplant" to look totally natural.