I don't see any reason why you couldn't amend the definition of compensation mid-year for employees who have not yet entered the plan.
However, the plan's definition of compensation for allocations does not (usually) control its definition of compensation for testing. You can use post-entry comp for testing without amending the plan. You can also use comp net of deferrals (remember to also net out sec. 125 deferrals if you do this). Just double check that there isn't something in your plan document that would lock you in to a particular definition of comp for testing.
If you think about it, though, allocation comp for deferrals is always post-entry comp; you can't defer on comp that was paid before you entered the plan.