Jack - yes, this is possible in many different ways. One that comes to mind:
Create an entity to contain the values you want in your navigation list (also create the forms to populate it). Place a datagrid on the page where you want the navigation list to display the navigation values. Create your microflow (to do something based on the literal value from your entity). Place the microflow behind a microflow button on the datagrid. If that button is the default button, it will be triggered with the object from the row you click or select (you can configure click or select, double click, single click, etc.)
Not sure exactly what you are trying to accomplish, but I am guessing that the built in Navigation tools in Mendix are not sufficient?
Hopefully this helps.