Just had an unfortunate accident in a multi-project solution where after adding a new project to the solution, writing some code and hitting F5
the project that ran
The F5 button is tied to whatever project is marked as "startup" and imho having VS "switch" startup project would be an awful feature and one of the first I'd disable after installing.
However, you can set a shortcut for starting new project instance via class view context menu, open Tools->Options->Keyboard and filter the list for "ClassViewContextMenus.ClassViewProject.Debug.Startnewinstance", set it's shortcut below for something handy like Alt + F5 (yes, you can replace just the F5 if you want). You can now run "current" project (project that holds currently focused source file or parent project of a file selected in the class view etc.) with this shortcut.