If you are using Avaya then it may be done by defining logic for the overflow itself, you can also use manual routing techniques such as AT&T routers.
The logic you can apply is,
Centre 1 agents on top skill and centre 2 agents on secondary skill.
If agents available count for centre 1 is less than 2 then you route calls to centre 2 agents on secondary skill.
This way you will always have atleast 1 agent availability in centre 1 to enusre SL% while all other calls will overflow to centre 2 to secondary agents.
Let me know if it answers the question.
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