Export Unsigned apk
means you will get the unsigned apk that is not signed by any keystore. A keystore is a binary file that contains a set of private keys. The app will need to be signed with a keystore to be used or installed using the Google Play App Store.
Export Signed apk
means you get the apk and it will provide the option to make the sign apk with existing keystore.
Android requires that all apps be digitally signed with a certificate before they can be installed. Android uses this certificate to identify the author of an app, and the certificate does not need to be signed by a certificate authority. Android apps often use self-signed certificates. The app developer holds the certificate's private key. More info here.