As I understand you want to launch the picture-capture software from your automation setup, perhaps you have a digital input that is triggered when a detector senses a possum walking past etc.
Using a servo, to press a key, or launching a mouse moving macro is NOT the way to do it though... It's like using a small remote controlled helicopter to fly accross the room and switch a light switch.. It's cumbersome..
So how to do it ?,
Your web cam, must have a DLL, or some library that can capture and image to a file via a command from you custom application.
I think you need to have an applicaiton that can listen on your serial port an/or poll your external device, and launch the camera image capture via a DLL, or a API, or some external library...
If you don't program, it may be a bit of work, but it is the only way to go, really.
If you want, I could do it for you in a couple of hours I reckon, you pick the language, and the operating system, tell me the hardware your using (connected to the serial port) and the web cam...