Multiple voltages off a single source
You would only need to daisy-chain them if the 5V regulator had a minimum load that could be met if followed by the 3.3V regulator. But keep in mind that the earlier regulators will need to supply both the current required for their rail as well as the current required for the later regulators.

Since the voltage drop is so large, using a switching regulator is recommended. The 80% or so (minimum, usually) efficiency from the switcher is much higher than what you can get from the linear. OTOH, if you were only dropping a single Li-ion cell to 3.3V-3.6V then a linear LDO regulator would be the way to go.