I think you should go back to the electrical conductivities of the two polymer (by taking in consideration their molecular weights). Then, you may find a relationship between their conductivities and their easiness in electro-spinning.
neither conductivity nor molecular weight play a role in electrospinning, but only particle size and quality of dispersion of the primary particles in the solvent you use for spinning. Please consider: what you prepare from PAni or PPy can not be a solution, will always at best be a dispersion, even if it looks transparent, it is not a true solution but a dispersion, you can look into my RG publications, enough evidence for this statement.
"molecular weight" determination had mainly been made by using wrong inappropriate technique (GPC) which can only be applied on truely soluble polymers.
As pointed out solubility plays an important role. It will also depend on what conductivity and mechanical strength is needed? . Otherwise nanocomposites with insulating polymers is also one option. The PS solution can be prepared and PANI can be added to that.
In-situ polymerization followed by doping can be tried.