Welcome to camera nerdery
Enable RAW image capture
You don't need to shoot RAW. In fact, you might try and it decide that JPEG is the way to go, but you owe it to yourself to try it. Not only will it give you uncompressed files, but it'll also give you a lot more flexibility when you're processing the images.
RAW processing is more complex than it is with JPEGs, so if you're totally new to the concept, it's best to set your camera to capture both in RAW + JPEG mode. That way, you'll have final JPEGs to share and RAW files to work with during the learning process. This will take up more space on your cards and your hard drive, but the payoff is worth it.
You may very well decide that the storage space or the extra processing work isn't for you and that's totally understandable. But, you owe it to yourself to give RAW a try and make that decision on your own rather than trusting blog posts. Feel free to totally ignore the RAW files until you're ready to start learning the workflow.
Switch off of auto mode
DSLRs are smart. So smart, in fact, that it's possible to get lazy and let it do almost everything for you. Switching over to creative exposure modes like Aperture priority, shutter priority, or even full manual will accomplish a few things. First, it'll get you thinking about the actual process of taking a photo. If you were shooting with a compact (or even your phone) before, there's a good chance you weren't setting your aperture and shutter speed. Using manual exposure will bring that to the front of your brain and hopefully keep it there.
Secondly, it'll help you learn the feel of your new camera. If you're in full-manual mode, you're going to have to be quick on the dials and buttons to get the proper settings for each shot. The more you use that stuff, the easier it'll be, so put the work in.
The one helper you can keep around is autofocus. You can switch over to manual if you want, but the AF systems in most DSLRs are complex enough that they have a learning curve of their own. AF is a very useful tool and being able to use it effectively can make a big difference in your photography.
If you find yourself getting frustrated, it's certainly OK to switch over to a more automatic mode. The last thing we want is for you to actually put the camera down. If that's the case, be sure to take advantage of the exposure compensation functions.
Learn the limitations of your camera
When stepping up to a DSLR or even an ILC from a compact or a phone, it's easy to set expectations a little too high. Yes, it'll be much better in low light and it'll focus a lot faster, but there are still limitations. Find a setting and take a shot at each ISO setting. Then find a situation with a different lighting arrangement and do the same thing. When you go back and look at the images on your computer, you'll have an idea of how it performs and which ISO settings work best for you.
It's also worth it to see how the autofocus handles very low-light situations. Get a feel for how high-speed the high-speed burst mode really is. Knowing about the little things will help you be better prepared for when it really counts.
Establish a photo filing system
If you were shooting a lot of photos before, you might already have this in place. In that case, well done. But for those who don't have their proverbial ducks in a row, things can get messy fast. Pick a central location to store your photos and a standardized naming convention for the folders and the images. Whatever software you're using to import your images should be able to help with this, even if you're using something free like Google's Picasa or Apple's iPhoto. Tag your images with useful info as you import them so they're easy to find later. Trust us. A new camera often means a huge increase in picture output and you don't want to have to go hunting through hundreds of photos for that one keeper.
Go shooting again
Once you know your way around the camera, all that's left to do is get back out there and shoot. A lot. But, don't be too frivolous with your frames. Yes, digital is "free" compared to film, but the shutter in your camera will only fire a certain number of times before it breaks. Most cameras have shutters rated for anywhere between 50,000 and 400,000. And while that sounds like a lot, if you keep it in high-speed burst mode, you'll be surprised how quickly they add up.
UPDATE: Reddit user, ascottmccauley points out that you should definitely write down your camera's serial number and save it somewhere as soon as possible. You should also go through the process of registering your new camera to make things a lot easier on yourself in case it gets stolen or needs to be serviced.
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