I'm a pilot with CAP in Arizona, and from my personal experience, the personality and 'vibe' can very greatly from squadron to squadron. Some squadrons are literally some old timers meeting at Denny's once a month and talking about airplanes. Others are much more serious and are very involved with SAR, Cadet Education, and promotion of aerospace in general. My squadron is fortunate to have many professionals in the emergency services profession, from FEMA, fire fighters, ADEM, and other agencies, including former and current military members as well. It really just depends on the squadron you join. Feel free to check out multiple squadrons if your area has more than one, so that you can find one that clicks with you. I believe we have around a dozen squadrons in the Phoenix area, so if you live in a large population center, there may be several for you to choose from.
It *can* be a lengthy process to get checked out and qualified in the airplane if you don't have someone to act as a good mentor for you and if you don't have the financial ability in the beginning needed to get checked out. If you find a good and highly active squadron, you can greatly speed up this process. But just like any other *volunteer* community service, they would prefer not to have a guy join just to take advantage of the inexpensive flying opportunities and not be a contributing member.
I'm thankful that my squadron is pretty large and very active in state services. Our aircraft (a C182R) gets flown about 20-30hrs/month and we get tasked with a wide variety of missions. I've flown SAR missions, photography missions for state agencies after local disasters (floods, accidents, etc), assisting border patrol in searching for 'northbound hikers', CAP Cadet/ROTC orientation flights, and many other tasks. This flying is all free and paid for the by the Air Force, the state, or CAP, respectively.
Once you are checked out in the airplane, you can fly it as you wish up to 100nm past your states border for $44/hour dry. In the 182, I usually average about $75-$85/hr wet when solo, but I'm usually able to split the cost with other pilots, which brings to me around $40/hr for flight in a high performance single. Not too shabby.
As far as adding ratings, what others have said is correct. Only thing you can't do is your initial PPL. Since you already have that, just make friends with a cfi who is in CAP and work something out.
Feel free to pm if you have any specifics you would like to know.