The elements of $S$ are conjectured to be $\mathbb{Q}$-linearly independent, and so a basis for the $\mathbb{Q}$-linear span of the multiple zeta values.
This is what Francis Brown accomplished at the motivic level. Actually, his proof via motives goes through the direction that is currently missing on the level of numbers, which is why it doesn't lead to an algorithm for writing down the (conjecturally unique) expression. In Theorem 7.4 of [Mixed Tate motives over $\mathbb{Z}$ (Ann. Math., 2012)], he proved that the motivic enrichments $\zeta^{\mathbb{m}}(\mathbf{s})$, $\mathbf{s} \in \{2,3\}^{\times}$ of the $\{2,3\}^{\times}$-zeta values are $\mathbb{Q}$-linearly independent. The dimension $d_n$ of the $\mathbb{Q}$-linear span $\mathcal{M}_n$ of the motivic MZV of a given weight $n$ is well known to be equal to the $z^n$ coefficient of $1/(1-z^2-z^3)$, which is also the number of expressions of $n$ as a sum of $\{2,3\}$-elements, and so the number of $\{2,3\}^{\times}$ zeta values of weight $n$. The linear independence of the $\zeta^{\mathbb{m}}(\mathbf{s}), \, \mathbf{s} \in \{2,3\}^{\times}$ then implies the equality: these elements form a basis for $\bigoplus_n \mathcal{M}_n$. There is a realization homomorphism $\mathcal{M} \to \mathbb{R}$ sending $\zeta^{\mathbb{m}}(\mathbf{s}) \to \zeta(\mathbf{s})$, and it follows (non-constructively) that there is a representation on the level of numbers.
However, proving $\mathbb{Q}$-linear independence remains completely out of reach on the level of numbers. We know very little here: even the irrationality of $\zeta(5)$ has remained an unsolved problem (for instance, see this MO question and answerthis MO question and answer).
What does follow immediately from the motivic formalism is the upper bound $\dim{M_n} \leq d_n$ of the conjectured dimension of the $\mathbb{Q}$-linear span of the weight $n$ MZV. This was proved independently by Terasoma and Goncharov; it means that there are many linear relations among MZV of a given (high enough) weight. Given that, identities like the weight $12$ one you quote should not come as a surprise. Explicit such identities were obtained by Gangl, Kaneko and Zagier. They are linked to modular forms of weight $n$, via Eisenstein series.