Google Voice is nothing like Skype. It’s a free service in which you get a phone number that you can set up to ring to one or more phones, and send/receive SMS messages for free (no short-code SMS or media messaging, though). You don’t make calls over the internet, you still have to use your cell minutes. Google Voice just presents the GV number as the caller ID when you call people.
It can do voice mail transcription for you, though the transcription can be hilariously bad sometimes. You can set up groups of contacts and have different voicemail greetings for each of them, or choose to send certain people straight to voicemail. My work phone number rings to my Google Voice, and I used to get a bunch of spam fax machine calls, so I set up a contact in Google Voice and added all the numbers that were spamming me, and configured Google Voice to play a “number is not in service” message for those numbers. I haven’t gotten a spam call in months now, I love it.
Apple won’t allow a Google Voice app, cuz they’re dicks. However, Google has a webapp that works excellently on the iPhone. You can go to http://m.google.com/voice to use it.
I personally love Google Voice. Voicemails play right in the webapp, and I use the iPhone app “Prowl” to get push notifications of new text messages/voicemails. It’s not an optimal user experience (thanks to Apple’s dickishness), but it’ll last me until my contract’s up and I can get an Android phone.