No, you cannot use the decoupling pin as a power supply.
What you can do is connect the 5V USB supply to VDDH and configure it to supply 3.3V to VDD. See also Regulator specifications, REG0 stage.
I see the VDD output can be configured to 3.3V, now my question is can I use this 3.3V as a power supply for external sensor and MCU?
Yes, as long as you adhere to Regulator specifications, REG0 stage.
Yes, as long as you adhere to Regulator specifications, REG0 stage.