Word of advice, don't use Li-Poly batteries unless absolutely necessary. They are way to sensitive to be charged by a DIY device. Charging Li-Poly batteries in series is also a problem. Since Li-Poly (Li-Ion batteries in generals) are very sensitive to overcharge you would need to balance individual cells during charging in order to avoid catastrophic failure. Take this for example, you are charging two cells in series, one cell is 3.8V, other is 4V, charger will run until voltage is risen to 8.4V, but since cells weren't balanced, one with higher starting voltage will end up being overcharged, damaged and at risk of exploding and setting everything around it on fire. Charging Li-Ion cells in series should be done with dedicated charger ICs.
As for the charging with DC-DC converter the answer is no. You can't have fixed voltage on DC-DC converter output while maintaining MPP voltage on solar panel. As long as battery can accept current from converter without its voltage crossing certain threshold, charger can operate in pure MPPT mode. When the voltage reaches that threshold charger must run voltage regulation, instead of MPPT algorithm.
I'll give you example with my charger (here's short video on YT
http://www.youtube.com/watch?v=pm8U1--0Bnw). If the battery (6V 4.5A VRLA battery) is drained, at full sun charger will manage to funnel as much as 0.8A into it (from 4.8W solar panel it manages to extract 5.7W). Charge voltage is temperature compensated but lets assume it is 7V. As the battery is charged, its voltage will steadily rise until it reaches 7V. When that happens charger will switch from MPPT to voltage regulation and maintain voltage at that level. MPPT will kick in only if the battery voltage drops below 7V, in order to bring panel to the MPP voltage or as close to the MPP voltage, where voltage regulation can take over. As the time passes voltage will be maintained at 7V, but current that goes into battery will steadily fall until the point where won't drop any further. VRLA battery can be maintained at that level indefinitely (this one has floating life rated at 5 years).
If you want fixed voltage for Li-Polys, you can put dedicated 3 cell Li-Ion charger/regulator IC at the output of DC-DC converter in order to charge batteries (relatively) safely. But if you put linear Li-Ion charger IC, MPPT running on DC-DC converter will be pretty much useless since charger IC will dissipate extra power as heat. As a solution DC-DC Li-ion charger would be better solution. Linear Technologies for example has DC-DC buck Li-Ion charger with fixed point MPPT but only for 3 cells
http://www.linear.com/product/LT3652. They are good but can be a real pain to solder (QFN-esque package).