There are some very easy things you can do to increase performance with so little work, it's easier to do them that see if you need to yet ;)
First and foremost is putting all static images and other media on a separate server. That eliminates a whole lot of queries on the boxen running the dynamic parts of the web server.
Next in line is make sure you are using as many hard drive spindles as possible. Of course you want your database on a separate machine, let alone a separate hard drive, but you also want your web server logs written to a separate hard drive. That prevents a lot of jumping around of the hard drive heads.
As far as "how do you know when you need to performance tune", I will give a different answer than George Stocker: When there is a cost associated with your performance that outstrips the cost of looking into it. I say it this way because your customers may be a little unhappy if your website is a little sluggish, but if it doesn't prevent anyone from using it, or recommending it to others, then it may not be worth looking into. People put up with sub-optimal performance all the time.