A common scenario: after you create a popup, you may want it to be visible only to people who haven't subscribed to your store, or other specified groups. Subscribers / Non-subscribers can help you achieve this requirement.
If you want the popup visible only to people who haven't subscribed to your store, please select "Visitors who are already in uShopAid profiles will not see the form". Even if a person does not log in to your store, we can still judge whether he is a subscriber or not, but there is a prerequisite: he used to log in to your website at least once in the current browser.
Note: The uShopAid app does not recognize the subscribers you added in the Klaviyo app, because the Klaviyo app does not sync its subscribers to the Shopify admin.
If you have created a List or Segment within the uShopAid app, you can set the popup to be visible only to people in specified List/Segment.