Choose ends like every captain, toss at first (5)
I believe the answer is:
elect
'choose' is the definition.
(electing is a kind of choosing)
'ends like every captain toss at first' is the wordplay.
'at first' suggests taking the first letters.
The first letters of 'ends like every captain toss' is 'ELECT'.
(Other definitions for elect that I've seen before include "Waiting to get into office" , "Put into power through the ballot box" , "Put in power by voting" , "Select; chosen" , "Vote to put into power" .)