libxml2 provides various examples showing basic usage.
http://xmlsoft.org/examples/index.html
For your stated goals, tree1.c would probably be most relevant.
tree1.c: Navigates a tree to print
element names
Parse a file to a tree, use
xmlDocGetRootElement() to get the root
element, then walk the document and
print all the element name in document
order.
http://xmlsoft.org/examples/tree1.c
Once you have an xmlNode struct for an element, the "properties" member is a linked list of attributes. Each xmlAttr object has a "name" and "children" object (which are the name/value for that attribute, respectively), and a "next" member which points to the next attribute (or null for the last one).
http://xmlsoft.org/html/libxml-tree.html#xmlNode
http://xmlsoft.org/html/libxml-tree.html#xmlAttr