The rules for BSG state that "Should the President or Admiral be revealed as a Cylon, the next player in the line of succession for that title claims it".
However, because of the Administration ability, it's possible someone could be president who already isn't first in line of sucession. If that person turns out to be a Cylon, do you really look at the "next" person on the line of succession list, or do you go back to the top and look for the "first" available person?