The MAC address is burned-in to the physical device by the factory. So regardless of what OS you are running on your PC you still have the one MAC Address. To have different MAC Addresses you should have different network cards. For example if your PC have Ethernet Port and WiFi Card then you have two addresses.
And changing your MAC address? The short answer is NO, you can't.
I haven't tried this but a quick search on the internet renders results like the following here. But note that it doesn't mean that you are changing your MAC address rather you are making it appear as if you have a different MAC address, that is just Virtual. If a device is communicating with your machine on the Datalink layer, it will still be able to see your original MAC address.