In this post Combining MS Office with GIS Nathan W suggests that com objects can be accessed from python, after a little digging I found http://www.codeproject.com/Articles/73880/Using-COM-Objects-in-Scripting-Languages-Part-Py which suggests that this is indeed the case.
If you can get an answer from Nathan W he might be able to give you some specific guidance.
C# and VB.net are much better at getting to the insides of ArcMap/Catalog but be prepared for a lot of lines of code and a bit of a learning curve. In python a lot of the methods are very simplified, but as necessary they are rigid. Programming in .NET makes you do all the little steps that are done in python simplistically and gives you the option of changing how it does things to suit your purposes.
I tell people who come to me for a program: I could write it in python in half a day and it will take minutes to run, or I could write it in .net in a day and it will take seconds to run! There is much more to programming than scripting but the end result will run much faster and there is a limit to what is feasible in python.
I recommend visual studio express 2010 like the one found here (I do not endorse this link, but you can find it on google) for ArcGis 10.1, it requires registration to a MSN account but apart from that it's free for non-commercial applications; when it's installed go back to your ESRI install media and install the correct developer kit... It's not installed by default and until you install your programming language it wont know which one to install.
Once that's done start a new ArcMap/ArcCatalog addin following these steps. The developer help that's installed with the SDK is a real source of knowledge with interfaces, samples and relationships; it's not so friendly to start but once you get into it it's great!
If you run into any difficulty with starting out there are plenty of samples only a google away and you could post on GIS.SE.