The most common and most likely answer to this crossword clue is the 5 plus 8 letter word FIRST OFFENDER
I've seen this crossword clue in The Daily Telegraph
F
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More clues leading to the result FIRST OFFENDER
Buddy explains!
The straight part
We know that "one who hasn’t slipped up before" is the straight/definition part of the clue. The straight part is often a synonym or definition, in this case one who hasn’t slipped up before = first offender.The cryptic/wordplay part
In cryptic crossword there's often an wordplay/cryptic part as well.This part involves a more complex hint, such as an anagram, homophone, hidden word, etc.
Sadly, We don't have an explanation for this specific crossword clue yet.