Semidirect product must satisfy 3 axioms:
(1) $N \unlhd G$ (2) $N\cap H = 1$ (3) $NH = G$
But clearly $\mathbb{Z_3} \cap \mathbb{Z_2} = \{0,1\} \neq \{0\}$, and it seems to be the case that $\mathbb{Z_3}\mathbb{Z_2} = \{0,1,2,3\} = \mathbb{Z_4}$ (by adding each element of $\mathbb{Z_3}$ with each element of $\mathbb{Z_2}$). So both (2) and (3) are not satisfied.
What is wrong with my argument?
The misunderstanding in your question is: how is $\mathbb{Z}/3\mathbb{Z}$ a subgroup of $\mathbb{Z}/6\mathbb{Z}$? It's not simply the subset $\{0, 1, 2\} \subseteq \mathbb{Z}/6\mathbb{Z}$, since this is not closed under addition: $1 + 2 = 3 \notin \{0, 1, 2\}$.
Instead, when you are considering $\mathbb{Z}/3\mathbb{Z}$ as a subgroup of $\mathbb{Z}/6\mathbb{Z}$, you are really identifying it with the isomorphic subgroup $2\mathbb{Z}/6\mathbb{Z}$. Similarly, $\mathbb{Z}/2\mathbb{Z} \cong 3\mathbb{Z}/6\mathbb{Z}$.