Head of school wears fur coat in capital (5)
I believe the answer is:
minsk
'capital' is the definition.
(capital of Belarus)
'head of school wears fur coat' is the wordplay.
'head of' suggests taking the first letters.
'wears' is an insertion indicator.
'fur coat' becomes 'mink' (mink is a kind of fur coat).
The initial letter of 'school' is 's'.
's' going into 'mink' is 'MINSK'.
'in' acts as a link.
(Other definitions for minsk that I've seen before include "Russian city" , "Capital of 15" , "Capital of Belarus" , "E European capital" , "City of Belarus" .)