Off topic - but relevant.
There's one thing I'll say about getting into the VA - "The sooner you enroll, the better". They can start a file on you 180 days prior to your effective date of discharge. "Service Connection" is the key. That's much easier to prove if you're still in the service than it is 20 years after you left. OIF/OEF veterans go to the front of the line. They may rate you 0% today when you're 25, but as long as the rating is there from a proven service connection, you now have a foundation if you find you can't walk when you're 50.
There are all kinds of vocational rehabilitation programs available, it all depends upon the veteran and the situation. Also something to note, a VA letter or rating may give you up to 10 "preference points" when applying for federal jobs. This CAN allow you to compete on the same footing (or in some cases, better) than people who are already working in the agency you're applying to.
Another concept to be aware of is "Concurrent Receipt". I don't think the law provides full implementation until 2014, but IIRC, any retired veteran above 50% will receive their full (taxed) retirement - PLUS - their VA disability (untaxed). Seems I remember being briefed last year that the implementation is phased starting this year. Still waiting on my own reevaluation to see how it works.
Also something to consider, if you don't like to deal with the bureaucracy yourself... While each VA hospital has what they call a "Patient Advocate" who'll work with you, but the bottom line is - they work FOR the VA, not for you. However, a number of Veterans' Service Organizations (VSOs - the VFW, American Legion, DAV, etc.) often will have a staff of knowledgeable people there at the hospital or nearby who'll champion your enrollment and claim and guide you through the process. They DON'T work for the VA, they work for you, but you have to sign a limited power of attorney to "hire" them to represent you in front of the VA. I'm fortunate I have a very experienced VSO rep taking care of me, I have to answer a telephone call once in awhile from him and find a document or two, but it's much quicker than waiting for the VA to send me letters telling me what I'm missing.
If you're a veteran and not enrolled already with the VA, get it done as soon as you can. Don't wait until you have a problem and no insurance.