Head in order earlier (5)
I believe the answer is:
prior
This could be a double definition.
'head in order' is the first definition.
'prior' can be an answer for 'head' (I have seen 'Religious head ' mean 'prior' so perhaps 'head' could also mean 'prior'). I'm not sure about the 'in order' bit.
'earlier' is the second definition.
(synonyms)
Can you help me to learn more?
(Other definitions for prior that I've seen before include "figure of authority in retreat" , "Previous - religious leader" , "Already arranged" , "English keeper" , "Pre-existing; head friar" .)