So I just purchased my first smartphone - an iPhone 4S.
Basic setup (contacts, ringtones, email etc.) is complete.

What do you recommend? I have an iPad so I am familiar with Apple and apps.
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Soundhound - If you're listening to the radio and you aren't sure what a song is, it'll identify it.
Pandora is really smooth operating too.

Tips:
From the "lock screen" double tap home button to bring up the camera. Slid the camera button up.

You can access Siri from the lock screen by holding home.

While listening to Music, at the lock screen, double tapping home will bring up Music Controls.

While in Camera, pressing + will take a picture when you have the phone horizontal.

Double tapping home while the phone is unlocked will bring up your latest apps.

Tell Siri who you're related to. Bring up Siri and say blank blank is my Wife. She'll have you approve it, that way you can tell her to text or call your Wife, and she'll know what person to call. You can also do it with Work, Home, etc.

That's all the tips I can think of, completely out of order.

Do you have a Case?
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:-)
Exactly the type of stuff I'm looking for in this thread. Some of what you posted I already knew but a fair amount is new to me.

Otterbox Commuter
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I had an otterbox on my iPhone after having one on my EVO. I got rid of it for a LifeProof case. They're about $30 more than an OB, but they're worth it. Seriously, if you can return your OB, do it and grab a Lifeproof case, you'll be glad you did. It's also a lot smaller than an OB.

They make a Phone completely Waterproof, Dustproof, Shock proof. I love my case, and tell everyone I can about it.

There is an app in the app Store that has a ton of tricks for the 4s. It's like .99 cents. I'll try to find it.

Edit: It's by Intelligenti LTD.
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+1 on the Lifeproof case. I had the otterbox defender and it was just too bulky and the silicone sleeve got stretched out of shape.
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He has the commuter, not the defender. IMO, an upgrade to the lifeproof may negate why he went with the commuter in the first place instead of the defender.
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Take a screen shot by holding the home button and the power button at the same time.
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Double tapping the button brings up the open apps function...scroll to the left (where the music control buttons are) and the far left icon locks your screen from auto-rotating. Handy when you're lying on your side trying to view your phone in portrait orientation.

If you don't use Apple's iCloud features...turn them off in the settings. They will drain your battery like crazy. (Side note: The one exception to iCloud syncing I have is for my "Find iPhone" app, it requires it to be on)
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Fun prank:

Bring up the dial screen, and take a screen shot. When someone asks to use your phone, bring up the screen shot, and hand it to them. :-)
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:-) that's funny
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The best advice I can think of is to NOT let my step-daughter touch it. It'll be broke in minutes, she's a screen smasher. I have no idea how she does it, I think she puts them in her back pocket and sits on them.
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These are great tips, especially the + button, it makes it so much easier to take photos.

Get a flashlight app, comes in handy more than you can imagine.

Powersaver: when phone is unlocked double tap the home button and it will bring up a task bar that shows all open programs. Press and hold one of the icons until they all shake and then you can close them by hitting the " - " sign that will appear. Keeping apps fully closed really will extend your battery life.
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Thanks for all the feedback, everyone. This really helps.
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I'm checking in here since these are all good tips for the iPhone 4 that I recently got. Also, ditto on the flashlight app.
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set up your phone with icloud so all your contacts, calendar, etc sync automatically. Comes in handy.
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if you plan to do any texting with it, turn autocorrect off immediately.
get the lifeproof case.
lock the touch screen before you put it in your pocket to avoit pocket dialing
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Use photo albums!
I have over 2100 photos in my camera roll right now becuase I didn't keep up with albums. Now I feel it is too late to back and move them all around.

I also recomend getting the Emoji app "Emoticons", you can set them up right into your texting keyboard.
Just don't send them to non-iphones or it will appear as chinese characters.
My favorite: Image or as a droid user may see it: Image
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You are so fancy now!! purrrrrrr :-)
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Never knew you could have photo albums, going to check that out now. I love the poop mountain!
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http://www.sinfuliphone.com/
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