First, using Access for a web database is not generally a great idea, particularly if you will have more than two or three people hitting it, or if the tables are large. However, there may be some reason you want to do it anyway, so here are a few things to think about:
1.) Windows server platform probably best for this attempt: It may be possible to use Access databases in a Linux environment, but I have not seen it done. I suspect it would be more complicated than the effort is worth. If you are working locally on a Windows box, cool. If you are using an ISP, I would check to see that their servers are Windows-based. (This has mostly to do with the way Access works; outside of Windows and the Access DLL's, mdb files are just files; you will have a lot of trouble using them elsewhere, I suspect.)
2.) Support for PHP Windows: Check to be sure that your ISP supports running PHP as an IIS CGI or module. If not, attempting to connect to an Access database will be much more difficult, I believe. I don't know that a lot of ISP's offer PHP on Windows IIS, but maybe yours does. If you're doing this on a local machine only, just be sure you've PHP installed and working correctly on Windows.
3.) Set up a DSN: Unless you have administrative privileges on your ISP you'll have to have them do it. Basically, they have to create a DSN (Data Source Name) which will be an ODBC link to your Access file. Get with the ISP to figure where and how they want your Access file uploaded, and then they can create the DSN for you. If you are working on a local Windows box, you can create the DSN yourself, referencing the local mdb file. The DSN will be an ODBC link to your local Access file.
4.) Use ODBC functions in PHP: You will have to use the generic ODBC functions for working with the Access DSN. PHP has no native support for Access.
Personally, if you're using PHP, I would not use Access. I don't say that because I hate Access; I have used it heavily over the years, and it has its place. However, Access is a Windows application intended primarily for local (not network) use. If I were you, I would download the MySQL Windows binaries (mySQL 4.0.7 rocks!) and install them on my Windows box, and use it instead. You can also download some good GUI tools like mySQL-Front, SQLYog for free. MySQL Studio and Mascon are two GUI products that are not free, but are very nice, and have fully function trial versions. These will give you some the same 'feel' while getting your feet wet. MySQL is used for nearly all PHP examples out there, and it's completely portable from Windows to Linux and back. Plus, it is a very powerful database server that will grow with your skills.
I think you will wind up being very frustrated trying to use Access for learning PHP, and if you are working with an ISP, you will probably go stark raving nuts.
If you have a lot of Access databases to convert, check out Access2MySQL from Intelligent Converters. It does a great job of making mySQL databases from existing Access files.
Hope this helps.