I disagree. While someone may not be able to make a given already existing poisonous substance any more effective you can certainly have a better understanding of both what makes it poisonous and effective to begin with and the processes of manufacture. This knowledge together can allow you to concentrate your production efforts into, say, the specific parts of a plant that provide the substance you want to put into your compound as well as distilling or concentrating processes to render purer or more uh concentrated substanced which would accumulate to give you more effectiveness per dose.
Remember this isn't a modern 'standard' manufacturing type of production. Individual methods of producing these substances can vary wildly and thus so can the effectiveness of the product you get from vendor 'A' from vendor 'B'. Really that is still the case today with products of different manufacturers, but perhaps to a lesser degree.
Several options occur to me. I think perhaps an interesting way to go would be to allow a person of greater skill to be more efficient with the source materials used to make the poisons, getting more base doses per unit of materials. Then produced doses of the poison could be concentrated/distilled into fewer doses to increase the DC, based on the number of doses that are concentrated and by what factor they are reduced.
This allows a poison maker of greater skill to choose between simply getting more doses for the same effort or making more effective poisons, with greater effort.