Can the plugin be used as an alternative way of exporting eShop order details?
Yes. As I write this, there are some order details that eShop Order Emailer exports better than eShop's built in order export feature (ie option chosen for each product sold).
The plugin wasn't designed to be used this way, but it does work pretty well. All you need to do is install the plugin, set which fields you want, and wait to receive an email. If you're in a hurry, you can hit 'Send Now' to get all the order details that haven't previously been sent to you. If you need all orders ever sent, then press 'Reset' and then 'Send Now'.