Abstract For a given C*-algebra $\mathcal{A}$, we establish the existence of maximal and minimal operator $\mathcal{A}$-system structures on an AOU $\mathcal{A}$-space. In the case $\mathcal{A}$ is a W*-algebra, we provide an abstract characterisation of dual operator $\mathcal{A}$-systems and study the maximal and minimal dual operator $\mathcal{A}$-system structures on a dual AOU $\mathcal{A}$-space. We introduce operator-valued Schur multipliers and provide a Grothendieck-type characterisation. We study the positive extension problem for a partially defined operator-valued Schur multiplier $\varphi $ and, under some richness conditions, characterise its affirmative solution in terms of the equality between the canonical and the maximal dual operator $\mathcal{A}$-system structures on an operator system naturally associated with the domain of $\varphi $.