As Rajesh suggested, you set multiple projects to start in a multi-project solution. To do this, select DEBUG -> Set Startup Projects (or right-click on the solution and select Set Startup Projects... from the context menu.
This will give you a window that lists all your projects in the solution. Check the "Multiple startup projects" radio button, and set the Action column to "Start" or "Start without debugging" for each project you want to run. You can use the up and down arrows to specify the order.
If your web application requires the service to be available when it starts (i.e., the web site calls the service during it's initialization/startup), you may be better off doing as you are now (running the WCF service from the command line), otherwise this should get you where you want to be.
Attached is a screenshot (VS 2012) with a solution similar to the one you outlined above: