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How does it work in 6th edition. Does it allow you to fire the same weapon twice?

No, it allows you to fire an additional weapon at full ballistic skill. Additional != the same weapon twice

nosferatu1001 wrote:
Additional != the same weapon twice

What?

!= means "not equal"

Being able to fire an additional weapon is not giving you permission to fire a weapon twice.

For example, a Land Raider moves 6" can only fire 1 weapon at full BS. The rest must Snap Shoot.
POTMS lets you fire an additional weapon (2 in this example) at full BS.

POTMS is the only way to make use of the LRR's flamestorm cannons if you move more than 6" as well, as template weapons cannot snap fire.