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This sounds like a horrible security risk. All someone would need to do is to set up an AP with the same SSID as your employer and they would automatically have access to your network traffic.
I know this doesn't answer your question but, if such an app existed, it would be dangerous to use.
This can be achieved regardless the agreement or not. Android already connects to saved wifi networks automatically. So anyone could set up an AP with the same name and phish, only if connecting to an AP depended on just the SSID. Wifi networks also have other identifiers like BSSID and MAC, which are more "unique" and are used by the OS to distinguish among wifi networks. Thus, android won't auto-connect to another AP with the same name unless he has connected to it before.This sounds like a horrible security risk. All someone would need to do is to set up an AP with the same SSID as your employer and they would automatically have access to your network traffic.
I know this doesn't answer your question but, if such an app existed, it would be dangerous to use.
The you to whom I was referring was you as an individual, not your employer. It is true that your employer's network traffic would only be exposed if you used your S4 on the rogue AP for something work-related.Why would this rogue AP with the same SSID have access to our network traffic? In the worse case, my S4 connects to this AP. No company's network traffic can be accessed by this AP.
If you were to read the actual agreement on your company's captive portal you would probably find they prohibit what you are trying to do. By connecting to that internet access you are agreeing to all terms and conditions of that agreement.
It's a pain to do every time, but there's a reason it's like that.