Usually HPLC has to do with stechyometry than molecular weight and chemical structure (molecules are just molecules and they do not carry any chemistry degree!).
That means that interaction inside a column has more to do with the actual structure, their shape, their electron clouds... in a chiral column, ligands are developed to interact with some parts of the structure, as Tom explained - they just fit better or worse!
Since enantiomers maybe defined as reflected images of each other, it is easy to close your eyes and imagine that they will in fact interact differently with some molecules at chromatographic bed.