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from it's abbreviation, Vlookup is Vertical lookup, as Hlookup is horizontal lookup
Vlookup for it's simple use is lookup at data and give the result, i use it for Recons mainly specially inventory reconciliation, i have the system item codes with the balance of each item at the end of the month, on the other side i have the fiscal count excel sheet at the end of the month too, i ask the excel to V lookup it each item balance in either the system or actual sheet on the other sheet, so lets suppose that's the item code is RM001 and it's system balance is100 , i'm telling him to give me the balance of this item on the other sheet and processed it vertically through column number whatever but you have to mention it in the formula and the range which should search such as a range of Cells and it will give me the balance in the other sheet for each item, if the balances is rows not column you can use Hlookup, i use it in GL recons too to get me the trial balances automatically every month to compare it with the sub transactions,
Pivot table is a tool to customize how you view the data or how the excel show it, summarize it, merge and extract, filtering, sorting, listing, totals, subtotals
http://chandoo.org/wp/2010/11/01/vlookup-excel-formula/
http://chandoo.org/wp/2009/08/19/excel-pivot-tables-tutorial/