Yes, such infinite subsets $A_0, \dots, A_{m-1}$ of an infinite group $G$ always exist. We can show this by wedging the problem into one of two polar opposite cases: abelian and ICC (i.e. every non-trivial element has an infinite conjugacy class).
Fact. An infinite group either has an infinite abelian subgroup or an infinite ICC quotient.
Proof. Let $FC(G) := \{ g \in G : [G : Z_G(g)] < \infty \}$ denote the FC-centre of $G$ containing those elements whose centralizer is of finite index, or equivalently whose conjugacy class is finite. For $g, h \in FC(G)$ we have that $Z_G(gh) \geq Z_G(g) \cap Z_G(h)$ and is also finite index, so $FC(G)$ is a subgroup of $G$ and in fact a characteristic one. There are two possibilities:
- If $FC(G)$ is infinite, then being an infinite FC-group (i.e. all conjugacy classes are finite) it contains an infinite abelian subgroup $\langle g_0, g_1, \dots \rangle$ constructed inductively: at each step, if the subgroup $\langle g_0, g_1, \dots, g_i \rangle$ is finite, then its centralizer is a finite intersection of finite-index subgroups hence finite index itself and thus infinite so we can find some $g_{i+1}$ commuting with and not contained in $\langle g_0, g_1, \dots, g_i \rangle$.
- If $FC(G)$ is finite, then $G / FC(G)$ is infinite and ICC since the conjugacy class of any non-trivial $g FC(G) \in G / FC(G)$ will contain the infinitely many images of the conjugacy class of $g$ in $G$.
$\square$
So it suffices to prove the existence of such $A_0, \dots, A_{m-1}$ with the additional assumption that $G$ is abelian or ICC (since after finding such sets in a quotient of $G$, any choice of lifts to $G$ will still have the desired property). We now show that we can choose inductively $g_0, g_1, g_2, \dots$ to put into the sets $A_0, \dots, A_{m-1}$ (say, cycling through the $A_i$) so that at each step the desired uniqueness holds.
Start by putting $g_0 = \dots = g_{m-1} = 1$ into $A_0, \dots, A_{m-1}$. Suppose we are choosing $g_n$ to add to $A_i$. There are two cases to consider for distinct words $a_0 a_1 \dots a_{m-1}$ and $b_0 b_1 \dots b_{m-1}$ that possibly give equal group elements that involve $g_n$ and otherwise only $g_j$ with $j < n$: (1) $a_i = g_n$ and $b_i \neq g_n$, and (2) $a_i = b_i = g_n$.
(1) simply rules out finitely many possibilities for $g_n$.
(2) is equivalent to the equation $g_n^{-1} (u^{-1} u') g_n = v (v')^{-1}$ that we get by rewriting $u g_n v = u' g_n v'$ for $u = a_0 \dots a_{i-1}, v = a_{i+1} \dots a_{m-1}, u' = b_0 \dots b_{i-1}, v' = b_{i+1} \dots b_{m-1}$. Note that $u^{-1} u' \neq v (v')^{-1}$ as otherwise picking $a_i = b_i = 1$ would then give distinct words giving equal group elements, contrary to our inductive hypothesis. If $G$ is abelian then there is no solution to this conjugacy equation so we have no additional constraints on $g_n$. If $G$ is ICC then the set of solutions is either empty (if $u^{-1} u'$ and $v (v')^{-1}$ are not conjugate) or is a coset of $Z_G(u^{-1} u')$. In the latter case this is a coset of an infinite-index subgroup, by ICC, because $u^{-1} u' \neq v (v')^{-1}$ so their being conjugate rules out $u^{-1} u' = 1$.
Both (1) and (2) only rule out finitely many cosets of infinite-index subgroups (in (1) we have cosets of the trivial subgroup!), so since we cannot write an infinite group as a finite union of such cosets by a result of B.H. Neumann (see MO question), there is some choice of $g_n$ for which neither (1) nor (2) can give a failure of the desired uniqueness, which completes the proof.