I've seen people start successful businesses without formal business training, so in the interest of reducing your time in school I think the MBA might be overkill. If you have a good business sense and are still an undergrad maybe you could tack on an Entrepreneurship minor if it's available to you. The people I'v seen start businesses were working in industry, saw a possible need, and used the knowledge they already had to make it happen so their situation is a little different.
As far as a sports supplement business, I guess it depends on what your goals are. If you are concentrating on creating novel products then it seems as though the PharmD will not cut it. You'll need some kind of pharmacology or medicinal chem PhD there to take care of the drug discovery, which it seems like a PharmD does not prepare you enough for in techniques and experience. I'm not sure exactly what medicinal chem entails but I believe some chem knowledge, perhaps more than a pharmacology phd would have, is necessary to find the best way to mass produce a drug in a cost effective way once it's discovered. All in all it sounds stressful, and unlike other fields like engineering where most of the cost is just computers and labor, making small businesses easier to start, scientific research can potentially require much more in material cost and facilities.
If the primary goal of your business is something other than creating original drugs such as simply selling them as a middleman or retail, then the pharmd will probably serve you better. Plus should things go sour, the pharmd is much safer to fall back on.
Also you are much more on the pharmd path right now since you've been a pharm tech for so long. Getting into a PhD program will require recommendation letters, usually a minimum of one is to be from someone you did undergrad research for. Also if you do undergrad research you can ask some of the grad students what they think and also find out how much they hate being Phd's. j/k...sort of
