Woman politely married first man (5)
I believe the answer is:
madam
'woman' is the definition.
(used to address a woman)
'politely married first man' is the wordplay.
'politely married' becomes 'm' (abbreviation, e.g. in genealogy. I am not sure about the 'politely' bit.).
'first man' becomes 'adam' (first man in the Bible).
'm'+'adam'='MADAM'
Can you help me to learn more?
(Other definitions for madam that I've seen before include "Titled lady" , "precocious schoolgirl?" , "How one may address a woman" , "Leader of House of Congress" , "Woman of standing" .)