The study of (quantum) phase transitions in heavy-fermion compounds relies on a detailed understanding of the microscopic control parameters that induce them. While the influence of external pressure is rather straight forward, atomic substitutions are more involved. Nonetheless, replacing an elemental constituent of a compound with an isovalent atom is---effects of disorder aside---often viewed as merely affecting the lattice constant. Based on this picture of chemical pressure, the unit-cell volume is identified as an empirical proxy for the Kondo coupling. Here instead, we propose an orbital scenario in which the coupling in complex systems can be tuned by isoelectronic substitutions with little or no effect onto cohesive properties. Starting with the Kondo insulator Ce$_3$Bi$_4$Pt$_3$, we consider---within band-theory---isoelectronic substitutions of the pnictogen (Bi$rightarrow$Sb) and/or the precious metal (Pt$rightarrow$Pd). We show for the isovolume series Ce$_3$Bi$_4$(Pt$_{1-x}$Pd$_x$)$_3$ that the Kondo coupling is in fact substantially modified by the different radial extent of the $5d$ (Pt) and $4d$ (Pd) orbitals, while spin-orbit coupling mediated changes are minute. Combining experimental Kondo temperatures with simulated hybridization functions, we also predict effective masses $m^*$, finding excellent agreement with many-body results for Ce$_3$Bi$_4$Pt$_3$. Our analysis motivates studying the so-far unknown Kondo insulator Ce$_3$Sb$_4$Pd$_3$, for which we predict $m^*/m_{band}=mathcal{O}(10)$.
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