I'm not at my machine to check, but don't the settings for each game include a fully customizable launch command for that specific game? I would think you could edit the launch command for your game however you want and then when you click play in steam it will launch your custom command instead.
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I found things online where you can replace the executable with a batch file and have that batch file launch both programs you want to launch. But I was hoping that there would be a way to just do it through the launch options. That would be easier to duplicate to different programs. I want to help some friends set it up and I can handle a batch file, but I don't want to have to create the batch file for all my friends on every game that we play that requires it..
Until someone is able to come up with a better solution, I just ended up setting it to launch with my computer, minimize itself to the taskbar, and disable the steam integration so that it doesn't track the playtime or whatever.