Even 3.3V nominal is likely "in spec" at 3.2V or even 3.1V, look at the datasheet.
Empty li-ion open-circuit voltage is around 3.4V. If load current is low (look at maximum peak, though; capacitors can only supply tens of microseconds, not milliseconds), like C/20 or lower, actual under-load voltage is close to that open circuit voltage.
This means, if you pick the downconverting regulator of lowest possible dropout (linear LDO with, say, 200mV of dropout, they do exist; or buck with highest possible duty cycle you can find, PFET-based can even go to 100%), you won't be losing any battery capacity.
If it is an absolute requirement that 3.3V rail must not drop even to 3.2V, then even with very low dropout, you might be losing some 5-10% of battery capacity. This isn't a bad deal to make, usually.
Buck-boost or SEPIC can fully utilize the charge, but remember, in low power sensor designs, it's always the quiescent current which dominates, so pick the regulator accordingly.