I will work with Kan complexes (i.e. fibrant simplicial sets) instead of CW-complexes. For the purposes of homotopy theory there is no essential difference: the homotopy category of pointed Kan complexes is equivalent to the homotopy category of pointed CW-complexes.
Let $\mathbf{Kan}_*$ be the (ordinary) category of pointed Kan complexes. As is well known, we have a functor
$$\pi_n : \mathbf{Kan}_* \to \mathbf{Ab}$$
for every integer $n \ge 2$. Slightly less well known is that we have a functor $$K (-, n) : \mathbf{Ab} \to \mathbf{Kan}_*$$
going in the other direction. The quickest way to define it is to say that $K (A, n)$ is (the underlying pointed Kan complex of) the simplicial abelian group corresponding (under Dold–Kan) to the chain complex $A [-n]$ that has $A$ in degree $n$ and $0$ otherwise. More explicitly,
$$K (A, n)_m = \bigoplus_{[m] \twoheadrightarrow [n]} A$$
where the direct sum is indexed over the set of monotone surjections $\{ 0, \ldots, m \} \to \{ 0, \ldots, n \}$, with simplicial operators defined as follows: for any monotone map $\alpha : \{ 0, \ldots, l \} \to \{ 0, \ldots, m \}$, given a monotone surjection $\beta : \{ 0, \ldots, m \} \to \{ 0, \ldots, n \}$ and an element $a$ of $A$, if $\beta \circ \alpha$ is surjective, then $\alpha$ sends $(\beta, a)$ to $(\beta \circ \alpha, a)$; otherwise $\alpha$ sends $(\beta, a)$ to $0$.
The Dold–Kan correspondence says that, for any simplicial abelian group $G$, we have a natural isomorphism $\pi_n (G) \cong H_n (C)$, where $C$ is the chain complex corresponding to $G$. In particular, we have
$$\pi_n (K (A, n)) \cong H_n (A [-n]) \cong A$$
naturally in $A$. This shows that $\pi_n : \mathbf{Kan}_* \to \mathbf{Ab}$ is essentially surjective on objects, while $K (-, n) : \mathbf{Ab} \to \mathbf{Kan}_*$ is faithful and conservative. With a bit more work it can be shown that $K (-, n) : \mathbf{Ab} \to \mathbf{Kan}_*$ is also full.
Of course, it should go without saying that $\pi_n : \mathbf{Kan}_* \to \mathbf{Ab}$ factors through the homotopy category to give a functor $\pi_n : \operatorname{Ho} \mathbf{Kan}_* \to \mathbf{Ab}$, which will be a left inverse for the functor $K (-, n) : \mathbf{Ab} \to \operatorname{Ho} \mathbf{Kan}_*$, which is full. Thus $\mathbf{Ab}$ is equivalent to the full subcategory of $\operatorname{Ho} \mathbf{Kan}_*$ spanned by the pointed Kan complexes that are homotopy equivalent to $K (A, n)$ for some abelian group $A$.
The case $n = 1$ requires some adjustments, but you seem to be familiar with that already.