In case you can use a somewhat philosophical explanation: $\leftrightarrow$ is a logical operator within statements, while $\equiv$ serves to state an equivalence between statements and thus may be thought of as meta-logical.
As Randall explained, $P \leftrightarrow Q$ is a statement $-$ one statement and a logical statement. The $\leftrightarrow$ will cause it to be true under certain truth value distributions for $P$ and $Q$. The same applies to $\neg(P \vee Q) \leftrightarrow (\neg P \wedge \neg Q)$.
For $\neg(P \vee Q) \equiv (\neg P \wedge \neg Q)$ however, you compare two truth tables, the one of $\neg(P \vee Q)$ and $(\neg P \wedge \neg Q)$, two distinct statements. If and only if both are true exclusively for the same truth value distributions, the equivalence applies and so the meta-logical statement $\neg(P \vee Q) \equiv (\neg P \wedge \neg Q)$ is true.