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I have the exact same situation you do in that I have Windows 7 at home and XP at work and I keep my libraries on a portable hard drive.
The simple answer to your question is, yes, any version of Calibre will be able to access and edit your library no matter which version it was created with or last edited with.
Since the newer versions of Calibre do have some features that I like to use I have it installed on my Win7 machine as well as the latest portable version on the portable hard drive. On my XP machine at work I have 1.48 installed and I have it directed to look for the library on my portable hard drive since it always assigns the same drive letter to the portable drive.
To do that right-click on the icon shortcut for Calibre on your XP machine.
Click on Properties
In the Target field enter "location of calibre.exe" --with-library "location of your library"
---In my case it looks like this: "C:\Program Files\Calibre2\calibre.exe" --with-library "E:\Calibre Portable\EditLibrary"
If you find that your computer does not always assign your portable drive the same letter then you will either need to tell Calibre where your library is every time you open it or install the 1.48 version of Calibre Portable on your drive and use that at work.
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