to answer your questions:
1) yes, it is relatively easy to pick up. however, as @Larry mentions, it still takes time and experience to master. i've been using it for 14 straight years, and i still feel like i know less than half of everything out there. of course, the Python universe continues to expand every day, so that may be the cause. :-)
2) Python is indeed portable, but as @Alex mentions, only POSIX systems (i.e., Mac OS X, Linux, *BSD, etc.) come with Python installed while PCs require a download, thus making PortablePython an option for moving around a directory tree which can be used for development. More specifically, you can use PyInstaller (multi-platform) or py2exe (PCs only; py2app is a Mac equivalent) to generate standalone executables that can be distributed to computers that don't require Python to already be installed.
To develop apps for MS Access, you will likely need to download the Python Extensions for Windows package (win32all) and use a COM interface. (Although I do not have an example of an Access app in my Python book, I do have COM client Python examples interacting with Word, Excel, PowerPoint, and Outlook in Chapter 23 of Core Python Programming.) A more modern alternative is to use IronPython on the .NET or Mono platforms. As far as UI stuff goes, win32all also gives you access to creating MFC apps.