Act as vicar maybe, providing church with a set of holy books (5)
I believe the answer is:
chant
'act as vicar maybe' is the definition.
(a vicar might chant)
'church with a set of holy books' is the wordplay.
'church' becomes 'ch' (common abbreviation).
'with' means one lot of letters go next to another.
'set of holy books' becomes 'NT' (abbreviation for New Testament).
'ch'+'a'+'nt'='CHANT'
'providing' is the link.
(Other definitions for chant that I've seen before include "(Ritual) incantation" , "Song (on the terraces?)" , "Repeated rhythmic phrase" , "Type of group singing" , "Vocal music" .)