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As with anything on a computer there are several ways to do this - some that are free, some that are not, some that are difficult, and some that are easy.
The first thing you need to note as you try to sync your two computers is their operating systems. Vista is notoriously difficult when it comes to doing things over a network, so you might want to go for an easier, paid solution if your new Tablet or PC has Vista.
Also, the solution will depend on the degree to which you want them synchronized. Here are a few different solutions to the problem of synchronization.
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Briefcases over a Network: Both XP and Vista contain types of folders called Briefcases. These folders are designed for this specific purpose of synchronizing two computers' files. To create a briefcase, simply right click in a folder or on your desktop and select "New" and then "Briefcase." Then place the files you want synchronized into the briefcase. Following this, connect your Tablet PC to the PC, either directly or over a network (here is a guide for how to do this). Drag the briefcase into the other computer over the network and it will create a copy of the briefcase on your Tablet. Now, every time you connect the Tablet to the PC you can synchronize the two folders so that changes in one will take effect in the other. Here is a more extensive guide to briefcases.
Paid Networking Software: If you are having trouble with Briefcases and want an easier solution there are a lot of applications that will let you share, synchronize, and connect two computers together. This will bypass all of the difficulties in connecting your two computers, automatically configuring everything for you--at a price. For example, Cisco's fantastic Network Magic will handle connecting the two (or more) computers and the sharing and synchronizing of files. It runs for about $50. Others include SmartSync and the freeware alternative Allway Sync.
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Through a USB Flash (Thumb) Drive: You can do synchronizing through USB flash drives a few ways. Certain USB drives are coming with built in sync software to handle the synchronization but as long as you have a U3 enabled flash drive you can install MigoSync, which will provide you with an interface to sync your Tablet with your PC. Otherwise, you can sync files using a briefcase created on your USB drive and then synchronized between the two computers, however this becomes more complicated since you are technically dealing with three places--so I recommend simply using MigoSync if you want to use a flash drive. The advantage to this is that you don't have to worry about the network issues and can simply plug your USB drive in each computer to complete the sync.
Keep your Files Online: This may seem like an odd solution but it probably the easiest and has the extra advantage of not taking any memory on your computer. There are many services which allow you to place files online and access them and edit them from there. The easiest of these is Google Docs, which would allow you to create documents from your Google account which you could access anywhere, simply by logging on. There are, however, more intense internet services that provide more versatility so that you could store a larger variety of files to access from either computer. These tools are created to be sharing and collaborating software but they have the extra ability of serving as a place to keep all of your files that you want to access and edit using different computers.