We describe a novel approach to prepare, detect, and characterize magnetic quantum phases in ultracold spinor atoms loaded in optical superlattices. Our technique makes use of singlet-triplet spin manipulations in an array of isolated double-well potentials in analogy to recently demonstrated control in quantum dots. We also discuss the many-body singlet-triplet spin dynamics arising from coherent coupling between nearest neighbor double wells and derive an effective description for such systems. We use it to study the generation of complex magnetic states by adiabatic and nonequilibrium dynamics.