To make us your favorite on the Web/Desktop App...
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Click on the small carrot in the lower left corner and then on Settings in the menu that appears.
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Click on the Preferences tab on the left side. Making Polymail your default app is the first option there:
To make us your favorite on iOS...
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Go to Settings
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Either scroll down the list of apps at the bottom, or
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Pull down to reveal the search bar and type Polymail
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Tap on Polymail in the list or the search results
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Look for the setting Default Mail App
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Tap Default Mail App
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Once in the menu, select Polymail from the list