As far as I understand, PostgreSQL adheres to the order in which you enter the columns when saving records. Whether this affects performance is debatable. PostgreSQL stores all table data in pages each being 8kb in size. 8kb is the default, but it can be change at compile time.
Each row in the table will take up space within the page. Since your table definition contains variable columns, a page can consist of a variable amount of records. What you want to do is make sure you can fit as many records into one page as possible. That is why you will notice performance degradation when a table has a huge amount of columns or column sizes are huge.
This being said, declaring a varchar(8192) does not mean the page will be filled up with one record, but declaring a CHAR(8192) will use up one whole page irrespective of the amount of data in the column.
There is one more thing to consider when declaring TOASTable types such as TEXT columns. These are columns that could exceed the maximum page size. A table that has TOASTable columns will have an associated TOAST table to store the data and only a pointer to the data is stored with the table. This can impact performance, but can be improved with proper indexes on the TOASTable columns.
To conclude, I would have to say that the order of the columns do not play much of role in the performance of a table. Most queries utilise indexes which are store separately to retrieve records and therefore column order is negated. It comes down to how many pages needs to be read to retrieve the data.