It is impossible to send two transactions that both spend the same output and have them both confirm.
Once an output is used in a transaction it is considered to be "spent" and can't be used again.
If you want to send a single transaction that uses the same outputs and sends bitcoins to multiple addresses, then you can just click this button:
If you want to create two competing transactions that both attempt to spend the same output, so that one transaction confirms and the other becomes invalid and vanishes, then you can use "createrawtransaction" in the console, and then you'll need to find a way to broadcast both transactions simultaneously to different peers. This is not an intended behavior for Bitcoin, so it won't be easy to do, but it is possible.