The molecular components of biological systems self-sort in different ways to function cooperatively and to avoid interfering with each other. Understanding the driving forces behind these different sorting modes enables progressively more complex self-assembling synthetic systems to be designed. Here we show that subtle ligand differences engender distinct M6L4 cage geometries - an S4-symmetric scalenohedron, or pseudo-octahedra having T point symmetry. When two different ligands were simultaneously employed during self-assembly, a mixture of homo- and heteroleptic cages was generated. Each set of product structures represents a unique sorting regime: biases toward specific geometries, preferential incorporation of one ligand over another, and the amplification of homoleptic products were all observed. The ligands' geometries, electronic properties, and flexibility were found to influence the sorting regime adopted, together with templation effects. A new method of using mass spectrometry to quantitatively analyse mixtures of self-sorted assemblies was developed to assess individual outcomes. Product distributions in complex, dynamic mixtures were thus quantified by non-chromatographic methods.