To access the App.Config you have to use the Settings object, in your case you should do the following:
First go to the PROJECT menu of Visual Studio - > Properties of (your project) , then when you enter you go to Settings and there you add the keys that you want to have available in your App.Config, I recommend at user level.
The App.Config would look something like this:
<?xml version="1.0" encoding="utf-8" ?>
<configuration>
<configSections>
<sectionGroup name="userSettings" type="System.Configuration.UserSettingsGroup, System, Version=4.0.0.0, Culture=neutral, PublicKeyToken=b77a5c561934e089" >
<section name="TuProyecto.Properties.Settings" type="System.Configuration.ClientSettingsSection, System, Version=4.0.0.0, Culture=neutral, PublicKeyToken=b77a5c561934e089" allowExeDefinition="MachineToLocalUser" requirePermission="false" />
</sectionGroup>
</configSections>
<startup>
<supportedRuntime version="v4.0" sku=".NETFramework,Version=v4.5" />
</startup>
<userSettings>
<OpenForiver.Properties.Settings>
<setting name="ClaveQueQuieroUsar" serializeAs="String">
<value>False</value>
</setting>
</OpenForiver.Properties.Settings>
</userSettings>
</configuration>
And in the code you call it like this:
this.Title = "text" + Settings.Default["ClaveQueQuieroUsar"];
And that's it, that's it.