Chap starts on Stitch in Lilo and Stitch (5)
I believe the answer is:
silas
'chap' is the definition.
'starts on stitch in lilo and stitch' is the wordplay.
'starts on' indicates taking the first letters.
The first letters of 'stitch in lilo and stitch' is 'SILAS'.
(Other definitions for silas that I've seen before include "Leader of the Jerusalem Church in Acts and Paul's companion" , "Chap" , "Book by George Eliot" , "George Eliot's Marner" , "Forename of miser" .)