Number 1: Seafarers
Buy this firstAdds: Ships, a pirate, gold fields, new islands to settle and a campaign of nine map setups.
Fixes: Long-time players find the same board stale; adds sea exploration.
Seafarers is the first CATAN expansion I'd buy. It adds islands and ships without making the game much heavier.
Usually a better fit for a different kind of group — still fine if it sounds fun.