Our web page is currently designed using the php-MySQL-Apache trio and I would like to begin working on an application that accesses the MySQL database directly. I am not exactly proficient in any language but have been administering a MS Access database for years. I am rather familiar with MS VBA. Any ideas on what direction I should take? Would Python be a good choice?

http://www.rekallrevealed.org/ might be worth looking into

As in a standalone local application? In that case you can use any language you want.

Well, you said you had PHP on there already, and that does a fine job of accessing MySQL (well, as fine as PHP does anything). Python would work just fine as well, of course. Perhaps a little more detail on what sort of application you are talking about will help us help you.

I was hoping to build a POS type front end. Something that we could run on a linux box to take orders. Basically the same as our online shopping cart but from a stand alone app.

For a standalone app, Python would do fine. PHP might do fine as well if you already know it, but I've never done PHP for anything but web stuff.

basically your choice of using mysql is irrelevant, there are plenty more important considerations to take into account, like HCI issues... graphical toolkits, hardware interaction... mysql is the least of your concerns

You can even use MS Access as a front end to connect to a mysql database.

How do you connect with Access? I have tried just fooling around but assumed it wasn't possible.

As much as I dislike access I have used this VERY successfully lately with end users querying a database via a web page but letting admin users use their existing access database

1) You need to download and install the MyODBC connector onto the client machine:
http://www.mysql.com/downloads/api-myodbc-3.51.html
2) Open "Control Panel -> ODBC Data Sources"
3) Add a data source - fill in the details as appropriate.
4) open a new access database (can be an existing one but test with a new one first)
5) Click "File -> Get External Data -> Link tables"
6) From the type drop down choose "ODBC"
7) On the window that opens click the second tab (forgot the name)
8) Choose the name of the datasource that you added then click ok
9) You then choose which tables you want to link.

From then on in you can just make macros, queries and forms as usual.

I wrote the above steps from memory but I think they should be roughly right.