I think I know what you're describing, which is just different connections of your meter leads to the cap sections?
*If* you have a dual section 100+100uF can, you cannot place those cap sections in series. It's not physically possible because they share a the negative terminal.
You might be measuring from one positive terminal to the other. Forget any reading you get there; in use, you will have a high d.c. voltage trying to polarize the cap in one direction. I'll bet a day's pay the cap will blow up when you switch the amp on the first time with this hookup (it *is* backwards of how typical non-polar electrolytics are made from a pair of polarized electrolytics). Typical non-polar electrolytics are made by connecting the positive leads together, and having individual negative terminals, which then become the 2 leads used for the composite cap.
Also, your measurement doesn't include any significant d.c., and will lead you to a wrong conclusion.
In the old days, Hewlett Packard made test gear where they needed to place electrolytic cap cans in series to obtain the needed voltage rating. 2 separate cans were used (even though each had multiple sections). The one with its negative terminal at ground potential was bolted to the chassis to make the ground connection. The second cap was place in series by connecting the can's negative terminal to a positive terminal on the first can.
The trick was that the can with the elevated negative temrinal voltage had to be mounted on an insulating phenolic wafer to isolate the can from the chassis (ground), and further had a cardboard sleeve that fit over the can so you didn't get shocked by 400v (or whatever voltage that can's negative is at) if you touched it.
Hewlett Packard had very clever engineering for their tube test gear in the 40's-70's. If they couldn't cheat and get a can cap to do what you're contemplating, I promise it's because it can't be done.