This question stems from trying to understand the notion of center of charge and if the analytical definition of this center depends on what exactly is minimized (the dipole moment or the total potential energy?). Which are the useful properties of the "center of charge" and how is it obtained in terms of a minimization procedure?
Optimisation problem: Imagine we have a distribution of positive charge $\rho(\mathbf{x})$ such that its support (the region where it is non-zero) is compact. Also, if we integrate $\rho(\mathbf{x})$ over the whole space we have a finite total charge $Q>0$. We now add a single point charge $-Q$. Where do we have to put it in order to minimise the total electric field?
Example (the trivial case): Clearly, if $\rho(\mathbf{x})=Q\delta(\mathbf{x-y})$, then the optimum is to put the negative charge in $\mathbf y$: in this case we can completely kill the total electric field everywhere: any other position will give rise to a dipole.
The general case: My feeling is that we have to consider the total potential energy of the resulting charge distribution and minimise it with respect to the position of the negative point charge... or do we have to try to minimise the dipole moment? The procedure should return the position of the "center of charge" of $\rho$. Is this always the case regardless of whether we try to minimise the total potential energy or the dipole moment?