It ends a shot as a substitute (7)

I believe the answer is:

instead

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'as a substitute' is the definition.
(I've seen this in another clue)

'it ends a shot' is the wordplay.
'it ends a' anagrams to 'INSTEAD'.
Though, I am unsure how this is indicated.

Can you help me to learn more?

(Other definitions for instead that I've seen before include "Alternatively" , "for a change" , "use this as a replacement" , "Rather - detains (anag)" , "In place (of)" .)

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