Is this grammar ambiguous?
We can consider $NUM$ and therewith $P$ a terminal symbol. Furthermore, $S$ does only occur once in every derivation. Therefore, if there is any ambiguity, it has to stem from

$\qquad \displaystyle S' \to\, = PS' \mid\, \neq PS' \mid \varepsilon$

Now, that fragment is a right-regular grammar with only one non-terminal whose right-hand sides do not share any prefixes. So clearly every term has only derivation, given by its length and permutation of $=$ and $\neq$.

In total, your grammar is unambiguous. Above observations also suggest that the grammar can be parsed in one pass from left to right with one token lookahead (distinguish $=$ and $\neq$). In fact, the grammar is basically a deterministic (no shared prefixes) and right-regular (replace all $P$ with $NUM$) grammar, so it's certainly an LL(1) grammar.

So I suggest you revisit the construction of the parsing table (your favorite textbook or Wikipedia) -- you must have made a mistake.