I present two similar ways to see this.
One way to see this, as others have observed, is to look at the orders of elements in the two groups. Since $S_3 \times S_3$ is a direct product, the order of an element $(g,h) \in S_3 \times S_3$ will be equal to the lowest common multiple of $g$ and $h$. Each element in $S_3$ has order $1,2$ or $3$, hence an element in $S_3 \times S_3$ has order at most $6$. But $D_{18}$ has elements of order $18$. Since two isomorphic groups must have the same orders for their elements, we conclude $S_3 \times S_3 \not \cong D_{18}$.
Note also that since $S_3 \times S_3$ is a direct product, we can construct an injective homomorphism
$$\rho: S_3 \times S_3 \to S_6$$
defined by
$$\rho((g,h))(i) = \begin{cases}
\rho(g)(i) & i=1,2,3 \\
\rho(h)(i-3) & i=4,5,6
\end{cases}$$
where a permutations $\sigma \in S_n$, $\sigma(i)$ denotes the image of $i$ under the permutation $\sigma$, for $i=1,\dots,n$.
Basically what I am saying is the following. Due to how in direct products the different parts of the tuples behave independently from each other, when we are given two permutations $g, h \in S_3$ acting on the elements $\{1, 2, 3 \}$, we can relabel $h$ so that it instead acts on $\{4, 5, 6 \}$. So, for example
$$\rho((1 \, 2 \, 3), ((1 \, 2 \, 3))) = (1 \, 2 \, 3) (4 \, 5 \, 6).$$
What this means is that $S_3 \times S_3$ can act faithfully on a set of size $6$, i.e. it occurs as a subgroup of $S_6$.
However, $D_{18}$ can't do this. If we were to embed $D_{18}$ as the subgroup of a symmetric group, we'd need to map one of its elements to an element of order $18$, which $S_6$ doesn't have. Indeed, $D_{18}$ naturally acts on a set of $18$ points, namely the vertices of an $18$-gon.