I cannot write in Tengwar. I believe there is a section in the Appendices to Lord of the Rings, however, with a fairly explanatory chart that should help you with it?
When to use... remember that it isn't a strictly-ruled form of writing, unlike our own, as it describes in Appendix B. It just has to sound like the word you're trying to write (although it's probably a good idea to be consistent whenever you write in Tengwar), basically; that might be of assistance to you if you're still in any way puzzled as to how to use a system of writing with no set spellings...
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