1. Click on the table to highlight it.
Go to the properties panel along the bottom of the Dreamweaver window.
Where it says Align, choose center from the list of available options. That will centre your table.
2. Try cell padding and spacing set to 1 and also the border set to 1 and see what happens.
3. Back to the properties panel again, where it says Bg color, Bg Image or Brdr color you can set the Background colour, Background image (be careful with that one) and the Border colour respectively.
4. By text colours on highlight I am assuming you mean that when you hover the cursor over the text it should change colour.
This can be applied to hyperlinks easily or to other text with a bit of fiddling. For hyperlinks, click on Modify (very top menu bar) and select Page Properties.
In there you can set text colours to use when the cursor hovers over a hyperlink.
5. Click in the table cell you want to adjust. Go back to the properties panel at the bottom of the program window. Change Horz and Vert to any alignment you want, which affects all elements in that cell. Each cell may be aligned differently to its neighbours.
The Window Sizes options catches everyone out sooner or later.
They remain greyed out and unavailable as long as the document you are working on is maximised. Click on the Restore Down option then drag the right, top and bottom of the document to a visible size within the main program window.
You can now use the Window Size options to view your page.
Go to Google and run some searches like this, depending on your version:
"dreamweaver mx 2004"+tutorial
Actually, you will only need either of that last two since some of the optins you discuss aren't available or are in different places in Dreamweaver MX (version 6).
Good luck with it.