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And the more I think it through, I can just keep a card saved on the Amazon account, so basically this question has turned into "what's the best grocery card?" which I'm sure has been answered a million times.
I just want her to have only one card to carry and use since I think she'll be willing to go along with that.
I don't agree with the above chart. If you have $300 in groceries per month, you have $250*0.05% + $50*.01% = $13 in rewards per month, which equates to $156 per year. For the Amex card, you get 6% back on the entire $300 per month, which gives $216 per year. However, you also have a $75 annual fee, which means that you're left with $141 per year. The catch is that you have a lot of variance in your spending, and the results change dramatically depending on how much you spend. If you're close to $300 most months, the math will hold up. If you're oscillating between $500 and $250, we may need to recompute.
Overall, Sallie Mae is probably the better option for your wife. As a perk, you get a 5% gas card and 5% off on Amazon.