What I found worked for me to acclimate to Android was using the menu button often, long pressing the screen often and when things got frustrating use the home button. Having a back button for the first time may also take a little bit to get used to. Being able to tell your phone which app to use by default also may take a bit of time to adjust to but it sure is nice. No longer will the browser, keyboard, camera, etc be decided for you by some nerd in a cubicle unless that nerd in that cubicle is you.
As far as any special things you might appreciate greatly, I'd suggest look on the Play store for toggle widgets or apps. Instant volume changing, brightness changing, radio on/off toggles are very handy on the fly.
I'd also suggest look at launchers. They are home screen user interface apps that allow you to truly make your phone you beyond the stock.
Have fun and welcome to Android and this forum.
A couple of apps I'd like to mention are Color Notes, for note taking, calendar, etc and Power Amp music player for taking your music playing ability to the next level.
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From a Beano