Here's one way,
You could set up an app config file or a txt file it doesn't really matter, what ever you are most comfortable with using and set a simple boolean value to True i.e
FirstTimeOpening = True
Then when your app is opened it can check this value, if it is true which it will be the first time, you can show your form, as the app is closing you can then adjust this value to false so that when the app opens and checks the value it will be false and won't show your start up form.