Hi Manoj,
Sorry for the confusion - the 3.3V rail is there for legacy support and not directly generated from the TinyDuino board. Instead, Vcc is the main power rail that you can use to power external devices, this is automatically selected between the +5V rail (such as when the USB is present), or VBatt when that is present. If you are running a coin cell, we'd recommend powering the other device using the Vcc or Vbatt pin. Note: If you are powering off the Vcc pin, if you plug in USB this pin will go up to 5V, so this may be an issue based on what you are connecting to. If so, just stick with using Vbatt.
Regards,
Ken
TinyCircuits