If you use the gmail interface you can show the FROM field to the proper email address. For other email clients, as long as it allows you to set the FROM field you are good to go.
Another option is to create a default email address for each domain under the account so if you have DomainA.com and DomainB.com in the account, create user@DomainA.com and user@DomainB.com. Then create the aliases under those two users. That way if you forget to change the FROM field, at least the email comes from the same domain. While it costs an extra $5 a month for the added user, it is a safeguard if you are concerned about forgetting.
The other benefit is that Google surprisingly has decent phone support for Apps for Business. I have had a couple issues over the years and a quick call got them resolved quickly. There is typically no wait time and you speak directly with a support person. Not really a deal breaker, but it is an added plus when evaluating products.