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rosserial will assume control over your serial port, so if that port is being used by something else -- and that 'something' is not a rosserial client -- that is probably not what you want.

Would I simply need to write my own ROS node and use pyserial (since I would be writing in python) to open the port and pass the message in?

If you're basically trying to convert ROS geometry_msgs/Twist msgs into something your remote system can use, then yes, you'll probably have to write a node that does this for you.

Please take the time to first search for an existing solution / implementation though, as it's likely someone (or multiple someones) has (have) already done this.