Analysing performance counters is complicated and takes a lot of practice, which is my way of saying that I am not experienced enough to give a complete list.
You are going to look for some specific things to start with.
First off is of course how long it takes to return the webservice calls. This tells you if you even have a performance issue at that load.
Next every one looks at CPU. This really does not tell you a lot however.
RAM is good, but you want to know how often your app is paging to disk, so check the Page Faults/sec.
Check your logical and physical disks for Current Disk Queue Length. If your physical disk is queing at all, you are reading/writing to much to the disk.
Beyond that you would normally be trying to find a specific and likely obscure problem.
I usually take performance testing in stages. Do a first test with the basics and if a particular page is having a problem look at the load it is causing.
If the whole production server is not performing adequately, it is easier to add more hardware, but I prefer looking at the code that is running and make that better.