Hi,
There are several options in the plugin that can work in your situation. But I would need some more details on what exactly you are trying to achieve in order to give you the right settings.
If guests can add products to the cart, checkout, and create an account at checkout, you need to disable the Block checkout option under the Blocking tab. Once they check out they will receive a verification email. You can choose to automatically verify the email of paying users. This option is under General > Account verification > Paying Customers
If you don’t want them to get automatically verified if they have paid, then please disable that option. In that case, in the plugin’s settings, Advanced tab you could explore options to Prevent login after checkout and you can also Block order emails. If you choose to prevent login after checkout, the user will have to verify their email to be able to log in. You can also choose to Block thank you page for non-verified users. If you choose to Block order emails, the user will have to verify their email first, then they would receive the order confirmation emails.
It is not possible to send an email for verification without creating the account first, whether this is through the My Account page or through WooCommerce Checkout. The plugin is meant to send verification emails after an account is created.