I'm not sure there is much point in buck-boost from single-cell lithium ion, as there is not much recoverable energy from the cell below 3.2V (which your "3.3V" rail could drop to without the system failing).
But as nctnico said, you just need to do the math. I would amend what he said, though, in that you can get switchers made specifically for low-power operation, maintaining reasonable efficiency down into the 1-10 mA region, with quiescent current far below a few mA. Just go to TI's web site, drill down to buck regulators with integrated switch, and have a look at the available Iq given your other requirements for packaging, input/output voltages, etc.
Another factor, somewhat counter-intuitive, is that micros with a large supply range usually draw less current at, say, 1.8V, than they do at 3.3V. This means that even if you obtain the micro's rail from a linear regulator ("LDO" in industry-speak), you still use less power overall. Any efficiencies gained from a switch-mode regulator are over and above that.