I do this all the time. I shoot annual school portraits and do 300+ heads at a time using a Chromakey background and get perfect results even on blonde wispy hair. I do NOT light the BG separately. But I do have a set of tried and true measurments that I use that work everytime.
First off I suggest using Savage tech 43 green paper. And two lights with umbrella modifiers at 45 degree angles to the opposite corners of the backdrop. Meter the subject at f/11 and the backdrop will be f/8 consistently across the entire width.
The suggestion of lighting the bg a stop brighter than the bg will cause spill from the green reflection coming back at the subject, having it one stop under eliminates this problem. I don't know why people keeping suggesting this method, It is backwards.
Another thing is that you must use custom white balance or the flash pre-set. Never use AUTO.
I have used many different extraction methods with this setup and never had issues with spill, I send the files to a lab and they do the knock out and send the proofs back with options to have 10 different backgrounds for the students to choose from. This is a simple, tried and true method that works very well. Trust me, I have done literally thousands of these images with this set-up.
Camera does not need to be 6 feet as I suggest below...it depends on your lens etc.
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