My 2 cents... others likely have different experiences and different opinions.
I have worked on the analytical chemistry side in laboratories in pharma, environmental (water/wastewater utilities) and food raw material manufacturing. Most of the people I've worked with have had a B.S. in a science field. A few have had a Masters, and a very few a PhD. For most manufacturing and water/wastewater lab positions, my opinion is that a Phd would be considered over-qualified. Pharma labs would probably have more positions appropriate for Phds, but most analysts I think you would find have either a B.S. or a Masters.
I think you have to decide where you want to head. For more research oriented jobs, be it in industry or academia, more education is likely to be an advantage. However, I believe there are relatively few of these jobs out there. For more process control, product release, compliance testing type labs, on-the-job-experience is likely to get you farther. My experience is that most lab jobs fall into this category.
I have worked in small labs (2-6 people) for the last 8 years. I would note that in my experience, the smaller the lab, potentially the more types of instruments and analyses you get to play with. I have used GC, HPLC, IC, ICP, FIA, TOC, etc, of course mixed with some good old fashioned tests like BOD, solids filtrations, etc.
Of course, whatever direction you choose now, it is likely at some point in your career you'll head off on some tangent you never imagined was an opportunity....