A real-space, multiple scattering method for calculations and interpretation of the Near-Edge Structure (NES) in X-ray absorption spectra (XAS) and electron energy loss spectra (EELS) is presented. The method includes core-hole and polarisation effects and is applicable to general aperiodic systems. The approach is based on simultaneous, self-consistent calculations of electronic structure and full multiple scattering NES and thus permits an interpretation in terms of structure and electronic properties such as charge transfer. The method is illustrated by comparison between theory and experimental EELS spectra obtained for hexagonal Boron Nitride (h-BN). Theoretical results concerning single walled h-BN nanotubes are also briefly discussed.