Plasmonic-organic hybrid technology affords the potential for exceptional bandwidth, extremely small footprint, and very low drive voltages resulting in substantially improved energy efficiency for devices. Optical loss is a well-recognized problem for plasmonic technologies but is currently addressed with some notable success. Thereby, the optimization of electrically poled organic electro-optic (OEO) materials is most critical since a large electro-optical coefficient allows implementation of short active device structures that result in lower insertion losses and lower voltage-length products. Most importantly, short structures also guarantee largest bandwidths and best energy efficiencies. Yet, an efficient optimization of in-device performance of OEO materials requires the development of novel computational simulation methods, especially as waveguide width dimensions reach tens of nanometers in plasmonic waveguides and as electrode surface/material interfacial effects become more and more dominant. The focus of this communication is on novel multi-scale modeling methods, including coarse-grained Monte Carlo statistical mechanical simulations combined with quantum mechanical methods to simulate and analyze the linear and nonlinear optical properties for high chromophore number density solid-state OEO materials. New chromophores are developed with the assistance of theory and may lead to an order of magnitude improvement in device performance.