A continuum theory is used to study the effects of homeotropic nano-particles on degenerate planar liquid crystal interfaces. Particle self-assembly mechanisms are obtained from careful examination of particle configurations on a planar film and on a spherical droplet. The free energy functional that describes the system is minimized according to Ginzburg-Landau and stochastic relaxations. The interplay between elastic and surface distortions and the desire to minimize defect volumes (boojums and half-Saturn rings) is shown to be responsible for the formation of intriguing ordered structures. As a general trend, the particles prefer to localize at defects to minimize the overall free energy. However, multiple metastable configurations corresponding to local minima can be easily observed due to the high energy barriers that separate distinct particle arrangements. We also show that by controlling anchoring strength and temperature one can direct liquid-crystal mediated nanoparticle self-assembly along well defined pathways.