Start by making sure your Arduino + shield is powered, and that the Bluefruit shield switch is set to Direct
Go through the pairing procedure so that you have a COM port for the Bluefruit shield. Keep note of the COM port name (for windows, as there's two, one in and one output - confusing!)
On Macs, pick the menu labeled EZ-Link, the one starting with cu.AdafruitEZ-Link
Windows, pick the outgoing COM port, usually the lower of the two numbers
Upload
That's it!
If you open and close the Serial Monitor you should see the Arduino reset (the L pin #13 LED will blink)
Upload sketches as you normally would via the Upload button
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