This is an accepted solution.
You can certainly have multiple stores, though each store would require a separate account. That said, if you use the same name and email address to sign up for both accounts then you'll be able to toggle between them easily via a dropdown when logged into your Admin.
If this is your first experience using Shopify, you may be interested in checking out our Intro to Shopify guide, along with our Getting Started guide. If you're thinking about using Print on Demand, when you're ready you can view all of your options here - personally I'd recommend Printful.
You can schedule a callback with our team via our support page. If callbacks aren't available at a certain time due to volume, you can also email us or start a live chat with us from that page. You can also send us a message on Facebook or Twitter any time, and we'll be happy to lend a hand there too! Feel free to add any questions to this thread as well and I'll be happy to reply as soon as I can. Cheers.